This study presents three studies that explore the ways in which multiple support sources (workplace and family social support) help individuals to experience work–life balance (WLB) and thereby develop a sense psychological availability and positive energy at work. We examine this serial mediation model across three population groups in Israel using time-lagged data from part-time students (sample 1), as well cross-sectional data from workers in the industrial sector (sample 2) and physicians in public hospitals (sample 3). The results indicate a complex process in which workplace and family support augment employee positive energy through WLB and psychological availability. The findings shed light on the importance of support from work and nonwork sources for the pursuit of employees to achieve balance in the spheres of work and life and suggest that the WLB helps in the development of psychological availability and augmenting employee positive energy.