Healthcare volunteers make important contributions within healthcare settings, including long-term care. Although some studies conducted in long-term care have shown that volunteers contribute positively to the lives of people living with advanced dementia, others have raised questions about the potential for increasing volunteers’ involvement. The purpose of this study is to understand volunteers’ perspectives on their work and relationships with long-term care residents with advanced dementia. A total of 16 volunteers participated in semi-structured interviews about their experiences. Interview data were analyzed using an inductive approach to thematic analysis. In this analysis, a central concept, relationships in dementia care volunteering, enveloped four related themes: mutuality and empathy as the foundation for dementia care relationships with residents, family as the focus of volunteer relationships, relationships shaped by grief, and staff support for volunteer relationships. We conclude that in long-term care settings, volunteer roles and relationship networks are more robust than they are often imagined to be. We recommend that long-term care providers looking to engage volunteers consider training and supporting volunteers to cultivate relationships with residents, family, and staff; navigate experiences of loss; and be considered as members of dementia care teams.