Context: Volunteers in palliative care settings are an essential part of care provision for patients and those important to them. Effective collaboration between volunteers and paid staff has been regarded as an important element of successful working, however, at times failures in coordination, information sharing and tensions within teams have been highlighted. Objectives: To explore the views expressed by volunteers and paid staff about their experiences of working together in palliative care settings. Methods: A systematic exploration of qualitative research using a meta-ethnographic approach. PsycINFO, CINAHL, Medline Complete, and AMED databases were searched from inception to December 2021 for the concepts “volunteers” and “palliative care.” Repeated in-depth reading and appraisal of papers identified metaphors and concepts, providing new interpretations. Results: Included papers (n = 14) enabled the construction of five storylines: 1) “we are the cake, and they are the cream”: understanding the volunteer role—separate, but part of a whole. 2) “…we don't know what's wrong with people but sometimes we need to know”: access to information and importance of trust. 3) “everybody looks out for each other”: access to paid staff and their support. 4) “…we don't meddle in the medical”: boundaries. 5) "it's the small things that the staff does for me that makes me feel good about my work": sense of value and significance. Conclusions: For effective working relationships between paid staff and volunteers, proactive engagement, recognition of each other's role and contribution, mutual sharing of information, and intentional interaction between both groups is needed.