Family is an important field for the formation of labor literacy among college students, but whether family resources can be transformed into labor literacy also depends on the individual's own psychological conditions. Based on 553 college student questionnaire data, this article distinguishes family social capital into internal relationship capital and external network capital, introduces core self-evaluation as the moderating variable, and uses correlation analysis and hierarchical regression to test its moderating effect. The results indicate that family social capital significantly and positively predicts various dimensions of labor literacy. The moderating effect of core self-evaluation is not significant in the dimensions of labor knowledge, labor attitude, and labor values, but is significant in the dimensions of labor skills and labor behavior, with the strongest moderating effect in the dimension of labor behavior. The simple slope test further shows that in the low core self-evaluation group, the predictive effect of family social capital on labor behavior is no longer significant. Family social capital has a stable direct transmission effect on labor concepts, while relying on the transformation of core self-evaluation for labor skills and behavior. College labor education should shift from unified supply to differentiated psychological support, helping students with low core self-evaluation to open up channels for the transformation of family resources into labor actions.