Few studies have examined employment outcomes in individuals with a primary diagnosis of posttraumatic stress disorder (PTSD). The current study used multivariate modeling to examine the relationship between PTSD, other aspects of military service, and employment among 5,862 veterans in a national Department of Veterans Affairs (VA) vocational rehabilitation program. Veterans with PTSD were 19% less likely to be employed at discharge (odds ratio = 0.81, p = 0.02) after controlling for potentially confounding variables. Individuals with substance use diagnoses or who were homeless at program entry were more likely to be employed at discharge, while receipt of public support income and severe mental illness decreased the likelihood of being competitively employed. This study supports current VA efforts to expand and improve the effectiveness of vocational rehabilitation services for veterans with PTSD.