Drawing on the self-determination theory, this study constructs a theoretical model to explore the mechanism through which employees’ perception of workplace renqing exerts positive spillovers to their family domain. In this model, workplace renqing perception serves as the independent variable, psychological need satisfaction and subjective vitality serve as two serial mediators, job stress serves as the moderator, and work to family enrichment serves as the outcome variable. Based on analyses of 300 observations from the scenario experiment and 288 responses from the two-wave survey of full-time employees, the results provide overall support for our hypotheses. The findings showed that workplace renqing perception has a significant positive effect on work to family enrichment; psychological need satisfaction and subjective vitality function as mediators as well as serial mediators; job stress not only negatively moderates the relationship between psychological need satisfaction and subjective vitality, but also negatively moderates the indirect effect of workplace renqing perception on work to family enrichment via psychological need satisfaction and subjective vitality.