Unpaid volunteers occupy many roles and provide crucial services in countries around the world. In Australia, for example, volunteers provide emergency response capabilities to most communities outside of major population centres. Despite the valuable function of this volunteer workforce, evidence indicates declining numbers of volunteer emergency service workers, and suggests that interactions between volunteering and family are implicated in falling numbers. The current study considered volunteering as one component of the community microsystem, and examined volunteering-related Work–Family Conflict (WFC) and Work–Family Facilitation (WFF) in N = 682 Australian volunteer firefighters. Structural equation modelling (SEM) analysis indicated that brigade operational demands had a negative indirect effect on intention to remain through volunteer WFC, as well as a concurrent positive effect on satisfaction. Two volunteering resources were considered (training opportunities and effective leadership), and had positive impacts on volunteer WFF through perceived developmental gain. Although developmental gain had a large positive impact on volunteer satisfaction, volunteer WFF did not. Results indicate that theoretical models of interactions between paid work and family can inform understanding of interactions between voluntary work and family, and thus links between community and family roles. Implications for volunteer emergency services organisations are discussed.