Trends indicate overall declines in numbers of volunteer emergency service workers and suggest negative organisational factors impacting adversely on volunteers and organisations. Conflict between emergency service work and family is implicated in falling volunteer numbers, and there is thus a need for research on difficulties experienced in balancing volunteer work and family. The current study tested an adaptation of the work-family conflict (WFC) model originally proposed by Frone, Russell, and Cooper, in a sample of 102 couples in which one partner was an Australian emergency service volunteer. Results supported a model in which volunteer work-related antecedents, including time invested in on-call emergency activities and post-traumatic stress symptoms, had indirect links with outcomes, including volunteer burnout and their partners' support for the volunteer work role, through the effects of WFC. These results add to research using theoretical models of paid work processes to better understand the problems faced by volunteer workers, and identify specific antecedents and outcomes of WFC in the volunteer emergency services. Implications for future research and organisations reliant on volunteer workers are discussed.