This study develops an understanding of the role of emotional connectivity for volunteer retention in prosocial business venturing. By embedding it in organizational ambivalence theory, our analysis of four volunteer-dependent community ventures reveals two mechanisms through which entrepreneurs strengthen volunteers’ emotional connectivity. We first identify emotion-focused practices that form volunteers’ emotional attachment to the venture, and then demonstrate how duality-focused practices, in the form of managing inherent organizational duality, complement emotion-focused practices to foster volunteers’ emotional loyalty to the venture. Theorizing from our findings, we introduce a model of managing volunteers’ emotional connectivity, and conclude by discussing its implications for prosocial venture research on volunteerism and affective commitment.