Although some organizations have formally introduced flexible work arrangements (FWAs) to enhance work–family enrichment, research indicates that informal organizational characteristics, such as perceived organizational support (POS) to utilize FWAs, may be more effective in achieving positive employee work and nonwork outcomes. Prior studies have established significant relationships between POS and work–family conflict. However, scarce research has focused on the underlying self-efficacy mechanisms linking POS to employee work and nonwork outcomes. Drawing on social cognitive theory and the job demand-control-support (JDCS) model, this article addresses this knowledge gap by examining how POS facilitates work–family enrichment through the mediating mechanism of self-efficacy to regulate work and life. To test the hypothesized mediation model, we collected self-report time-lagged data from 253 public-sector and private-sector employees in Australia. Structural equation modeling (SEM) results revealed that POS positively predicted self-efficacy to regulate work and life, in turn leading to work-to-family enrichment (WFE; development, affect, capital) and family-to-work enrichment (FEW; development, affect, efficiency). Evidence of these relationships across two time points was demonstrated, emphasizing the synergistic combination of POS and dynamic processes of self-efficacy to regulate work and life in facilitating work–family enrichment