Drawing on the psychology of working theory (PWT), the present study was performed to evaluate the predictor session of the PWT and career exploration behavior with a sample of Chinese nursing college students from diverse backgrounds. The research employed a cross-sectional research design and 854 nursing students were recruited from one health vocational college situated in Northwest China. Structural equation modeling was utilized to conduct the analysis; confirmatory factor analysis and structural model testing were performed accordingly. Moreover, mediation analysis that used bias-corrected percentile bootstrapping method and moderation analysis were carried out in accordance. Overall, most of the proposed direct paths were significant, but the mediation results were mixed. Proactive personality simply moderated the impact of economic constraints on career adaptability. The results suggest that PWT is applicable to nursing college students and the model is generally supported in the Chinese context. It is the first empirical work that used this model among nursing college students and future decent work perceptions contributed another important antecedent of career exploration behavior. The practical implications based on these findings are provided as well.