Although research has demonstrated the benefit of psychological detachment for employee well-being, the explanatory mechanisms related to work behaviors underlying this effect remain underdeveloped. Addressing this research gap, we consider self-discrepant time allocation (preferred–actual allocation) as a mediating mechanism through which psychological detachment affects employee well-being. We hypothesize that psychological detachment is associated with self-discrepant time allocation at work. Specifically, we suggest that employees with low detachment tend to allocate more time than preferred to work activities that demand fewer self-regulatory (...) resources, and allocate less time than preferred to activities demanding greater self-regulatory resources. These self-discrepant time allocations at work are associated with employee well-being. Polynomial regression analysis and response surface methodology were used to test the hypotheses. The results, based on a sample of 390 faculty members from 19 universities, showed that, when psychological detachment during weekends is low and self-regulatory resources are insufficient, employees will allocate less time than preferred to work activities that require more self-regulatory resources (i.e., researching activities) during the subsequent work period. Instead, employees tend to allocate more time to activities that require less resources (i.e., teaching activities). These discrepancies between actual and preferred time allocation at work activities, in turn, negatively affect employee well-being and mediate the relationship between psychological detachment and employee well-being. (shrink)