This study examines participation in Unemployment Insurance (UI) and Employment Services (ES) by adults who received cash welfare benefits through Temporary Assistance for Needy Families (TANF). Among those who leave TANF for employment the study measures the rates of subsequent unemployment, application for UI, eligibility for and receipt of UI benefits, and the use of Wagner-Peyser funded ES. The study also investigates the correlations between UI and ES services receipt with reemployment and future independence from TANF. The analysis is based on person-level administrative program records from four of the nine most populated states [Florida, Georgia, Michigan, and Ohio] between 1997 and 2003. Evidence suggests that three-quarters of new TANF leavers experience unemployment within three years, and one-quarter of the newly unemployed apply for UI benefits. About 87 percent of UI applicants have sufficient prior earnings to qualify for benefits. However, only about 44 percent qualify based on their reasons for job separation. Among UI applicants, TANF leavers had much higher rates of voluntary quits and employer dismissals than did non-TANF leavers. Nevertheless, 50 percent of TANF leavers who apply for UI ultimately receive benefits. Public ES are used by one-quarter of newly unemployed TANF leavers. More than three-quarters of UI applicants use the ES whether they receive UI benefits or not, while 14 percent of newly unemployed TANF leavers who do not apply for UI choose to use ES services. Among TANF leavers who become unemployed and apply for UI, the rate of return to TANF is lower for those who receive UI benefits. Rates of return to TANF are highest among non-beneficiary UI applicants, and non-UI applicants with low recent earnings. A characteristics analysis of these groups provides a guide for targeting job retention and advancement services to TANF leavers.