Although the direct effects of work–family enrichment on satisfaction are well-documented, previous theoretical predictions and empirical findings of the relationship have been inconsistent. Drawing on social cognitive theory, the current research examined how work–family enrichment contributes to job and family satisfaction by exploring the mediating mechanisms of self-efficacy and work–life balance. This study also empirically validated a new self-efficacy measure using the work–life interface nomological network. A heterogeneous sample of Australian employees (N = 234) from four different organisations responded to two waves of data collection separated by a 12-month interval. Using structural equation modelling, the results of the statistical analysis provided preliminary support for the hypothesised chain mediation model and the newly developed five-item self-efficacy to regulate work and life scale. Specifically, work-to-family enrichment and family-to-work enrichment were positively related to self-efficacy, which in turn had a positive effect on work–life balance. Similarly, work–life balance had a positive impact on job and family satisfaction. Evidence of these relationships over time was demonstrated, thereby emphasising the importance of person–cognitive resources (e.g. self-efficacy) in influencing life outcomes. Validation of the self-efficacy scale also demonstrated robust psychometric properties and criterion validity. Implications of these results were subsequently discussed.