Rapidly decarbonizing our way of life, parti¬cularly the way we generate power, will be critical to mitigate the potentially catastrophic effects of climate change. Time is of the essence and low-cost and scaleable energy technologies that are equitable can play a key role in these efforts. Organic photovoltaics (OPVs) are an emerging technology based on semiconducting organic polymers and molecules with many potential benefits, such as low weight, flexibility, and printability. In recent years, the performance of research level OPVs has significantly increased, closing the gap to established silicon solar cell technologies. Arguably, printability is one of the key advantages of OPVs, as it can facilitate high-throughput production at extremely low cost. Yet, producing high efficiency OPVs with scaleable production methods such as roll-to-roll (R2R) printing is a key challenge that remains on the path to commercialization and implementation of OPVs. This is largely due to the fact that the efficiency of OPVs strongly depends on the complex microstructure -- also referred to as morphology -- of the active layer that converts light into electricity. Controlling the self-assembly of the materials during printing is significantly more challenging on the industrial scale than on the lab scale. In this thesis, three morphology control strategies are developed that enable direct transfer to scaleable printing techniques while maintaining high solar cell efficiencies. The focus of this work is on developing structure-performance relationships using a suite of synchrotron X-ray scattering techniques for in-depth morphological characterizations. Further, we use these techniques to study the self-assembly of the active layer in real-time during printing and provide mechanistic insight on how different morphology control strategies can be leveraged to optimize the morphology and thereby the performance of printed OPVs. First, a high-level introduction outlines the challenge of rapid decarbonization and the role emerging solar cell technologies such as OPVs can play in addressing this challenge. Special emphasis is placed on the challenge of scaleability on the path to commercialization of OPVs. Chapter 2 provides relevant theoretical background on the three key areas relevant to this thesis research. (I) Organic solar cells, (II) X-ray characterization techniques for organic thin films, and (III) scaleable printing techniques for organic solar cells. Chapter 3 describes a systematic side-chain engineering molecular design approach to control the self-aggregation of a widely used OPV acceptor polymer enabling high performance printable all-polymer solar cells. We find that a balanced propensity of donor and acceptor to self-aggregate is key to achieve intrinsic printability for this material system. Specifically, we show a simple yet effective way to modulate the self-aggregation of the commonly used naphthalene diimide (NDI)-based acceptor polymer (N2200) by systematically replacing a certain amount of alkyl side-chains with compact bulky side-chains (CBS) resulting in a series of random copolymer (PNDI-CBSx) with different molar fractions. Both solution-phase aggregation and solid-state crystallinity of these acceptor polymers are increasingly suppressed with increasing molar fractions of the CBS side-chain. We find that balanced aggregation strength between the donor and acceptor polymers is critical to achieve high-performance (up to 8.5% efficient) all-PSCs with optimal active layer film morphology. Further, we show that balanced aggregation strength of donor and acceptor yields an active layer morphology that is less sensitive to the film deposition methods and solution coating can be achieved without performance losses. Chapter 4 showcases the systematic fluorination of a PBDB-TFy donor and PNDI-TFx acceptor polymer (x, y = 0, 50, 75, 100) and discusses the impact active layer morphology and device performance. We find that fluorination of donor and acceptor polymers does not significantly alter the crystallinity of the respective neat polymers but results in increased compatibility -- in terms of reduced Flory-Huggins interaction parameter -- of the materials. We observe a systematic increase of device performance with increased extent of fluorination. Morphological studies reveal that this improvement largely stems from a more favorable blend morphology with reduced domain size. Specifically, we characterize the domain size of the best performing blend PBDB-TF100:PNDI-TF100 in detail with RSoXS and HRTEM techniques. We observe good agreement between both techniques yielding a domain size close to 30 nm representing a significantly reduce phase separation compare to the non-fluorinated control system PBDB-TF0:PNDI-TF0. Further, we explore the device optimization of this system with the commonly used DIO additive in detail and find that DIO selectively interacts with the donor polymer leading to increased face-on texture crystallinity, further improving the fill factor of the solar cells. Chapter 5 provides in-depth mechanistic insight into the in-situ morphology evolution of all-polymers solar cell systems during scaleable printing. We demonstrate how non-covalent interactions between donor and acceptor polymers can be leveraged to achieve a morphology evolution that is insensitive to changes in the drying conditions and that translates exceptionally well to printing fabrication. Specifically, we systematically control the donor-acceptor interactions using different extents of fluorination of PDBD-TFy and PNDI-TFx (x, y = 0, 0.5, 1.0) donor and acceptor polymers. We show that donor-acceptor interactions can induce donor crystallization, facilitating a high solar cell fill factor (0.65) and excellent transferability to printing fabrication. Leveraging this molecular design strategy, we fabricate printed devices with up to 6.82 % efficiency (compared to the 3.61 % efficient control system). Chapter 6 showcases a novel solvent additive approach based on phthalate additives to control polymer crystallinity and suppress unfavorable phase separation in a representative PTB7-Th/P(NDI2OD-2T) all-polymer solar cell. The best-performing additive increased the blade-coated device performance from 2.09 to 4.50% power conversion efficiency, an over two-fold improvement, mitigating the loss in performance that is typically observed during process transfer from spin-coating to blade-coating. We find that the improved device performance stems from a finer polymer phase-separation size and overall improved active layer morphology. Real-time X-ray diffraction measurements during blade-coating provide mechanistic insights and suggest that the dioctyl phthalate additive may act as a compatibilizer, reducing the demixing of the donor and acceptor polymer during film formation, enabling a smaller phase separation and improved performance. Chapter 7 concludes this thesis with a summary of key conclusions and future directions of this work. Specifically, mixed phase characterization and morphology evolution of polymer:NFA systems, potential morphology control strategies for state-of-the-art all-polymer solar cells, and solvent quality and temperature aggregation studies are briefly discussed. Lastly, the appendix to this thesis provides an overview of selected examples of structural characterization of functional organic thin films to develop structure-property relations in organic solar cells and adjacent field such as organic field effect transistors (OFETs).