This paper draws on wider research into the uneven spatialities of emergency services for homeless people in England, and focuses on the role of volunteers in staffing these spaces of care. In the first part of the paper, we explore the contemporary context of voluntarism, locating opportunities for volunteers in the shifting nature and character of organisations providing these services. We also trace conceptualisations of motivational underpinning of volunteering, arguing for the inseparability of giving and receiving in this context. These discussions frame the second part of the paper where we use interview and participant observation research to discuss what motivates volunteers to identify with and serve homeless people. The paper interprets the discourses, practices and performances of volunteering in services for homeless people in order to understand how volunteers are implicated in the co-construction of spaces of care.