The school-to-work transition can be extraordinarily challenging in the turbulent labor market, and the uncertainty about employment outlooks can cause intense anxiety for college students. Drawing from psychology of working theory (PWT), the current study examined the predictor section of the PWT model in relation to employment anxiety with a sample of impoverished undergraduates in China ("N" = 362). Findings suggest that (1) economic constraints were negatively associated with work volition and future decent work perceptions; (2) work volition mediated the relation between economic constraints and future decent work perceptions; (3) future decent work perceptions were negatively related to employment anxiety; and (4) proactive personality and social support attenuated the adverse influence of economic constraints on work volition. Overall, this study contributes to PWT by adding a new outcome (employment anxiety) and also providing evidence of moderation effects. Implications for universities and career counselors are discussed.