The ability of welfare-to-work clients to leave the welfare rolls and stay in the labor force is often limited by the work barriers they face. Using a sample of 1,404 female welfare-to-work clients we first examined the structure of work barriers and then tested their contribution to current work status in the context of a structural equation model that incorporated other central pathways to employment. Whereas work barriers included diverse factors ranging from lack of transportation to low quality jobs, they were shown to constitute a uni-dimensional construct. Furthermore, work barriers had a net adverse effect on employment outcomes, controlling for job search self-efficacy and employment intention. We conclude with discussion of implications for the development of welfare-to-work programs and interventions that target low-income women. [PUBLICATION ABSTRACT] The ability of welfare-to-work clients to leave the welfare rolls and stay in the labor force is often limited by the work barriers they face. Using a sample of 1,404 female welfare-to-work clients we first examined the structure of work barriers and then tested their contribution to current work status in the context of a structural equation model that incorporated other central pathways to employment. Whereas work barriers included diverse factors ranging from lack of transportation to low quality jobs, they were shown to constitute a uni-dimensional construct. Furthermore, work barriers had a net adverse effect on employment outcomes, controlling for job search self-efficacy and employment intention. We conclude with discussion of implications for the development of welfare-to-work programs and interventions that target low-income women.