Built on the job demands-resources model (JD-R) and self-determination theory, the present research proposed that the relationship between work resources (social support) and employees’ work engagement takes on an inverted U-shaped curve, and presents a model of the moderation of personal resources (psychological capital) on the relationship. The hypotheses were tested by hierarchical regression analysis and path analysis with 535 surveys collected in 19 enterprises. The findings demonstrated an inverted U-shaped curve relationship between enterprises’ social support and employees’ work engagement and further suggested that the predicting effect of social support on work engagement is influenced by employees’ psychological capital, that is to say, the transformation from social support to work engagement bears higher efficiency in employees with high psychological capital than in those with low psychological capital. However, psychological capital fails to display a moderating effect on the curve relationship between social support and work engagement. The present study, casting doubt on the assumption that enterprise supply must meet the needs of employees, argued that the effectiveness of enterprises’ resource support is influenced by the individual needs of employees.