An abundance of research shows the benefits of participation in volunteer work for individuals, employers and the society as a whole. However, relatively little is known about the precursors of volunteer work. In this study, we aim to fill this gap by investigating to what extent work‐related well‐being can function as a driver of volunteer work. Moreover, building on the Conservations of Resources Theory (Hobfoll, , ), we propose that the relationship between work‐related well‐being (burnout and engagement) and volunteer work is mediated by the work–home interface (work–home enrichment and work–home conflict). This hypothesis was tested in a large Swiss sample (N = 1947). Consistent with our expectations, structural equation analyses revealed an indirect relationship between (i) work engagement and volunteer work via work–home enrichment and (ii) between burnout and volunteer work via work–home conflict. In conclusion, it seems that well‐being at work indeed functions as a precursor for volunteer work because of the consequences it has for the work–family interface. Copyright © 2016 John Wiley & Sons, Ltd.