With increased blurring of boundaries between work and family lives, work–family segmentation has been suggested as an effective work–life strategy for social workers who are involved in complex human service work, to reduce work–family conflict and enhance work–family enrichment. Yet, numerous studies have examined social workers’ work–family conflict experiences, and only a few have focussed on social workers’ work–family enrichment experiences. Correspondingly, drawing on boundary theory, conservation of resources theory and work–family enrichment theory, we investigated how family-to-work enrichment and work-to-family enrichment help social workers to benefit from work–family segmentation to increase their job performance. Using an online survey of Australian social workers (n = 504), we tested the impact of work–family segmentation on the job performance of social workers through family-to-work-enrichment and work-to-family enrichment. The study found evidence for the positive impact of work–family segmentation in helping social workers to experience family-to-work enrichment and work-to-family enrichment, thereby enhancing their job performance. The theoretical and practical implications of the findings for social workers, supervisors and the social service agencies are discussed.