Background Faced with rising needs for patient support, palliative care is shifting towards a more community-based approach. Yet the profile of volunteers in this field is poorly known. Aim To explore psychosocial characteristics of palliative care volunteers, by comparing them to two groups, volunteers from the health and social sector without contact with palliative patients, and people from the general population without volunteer activity. Design Observational comparative study. Data were analyzed using descriptive statistics and logistic regression analysis. Participants The 3 groups of participants were recruited in France between September 2020 and June 2021. They completed an online survey assessing sociodemographic characteristics and psychological resources (self-efficacy, hope, optimism, resilience, mindfulness, self-compassion, empathy, forgivingness, and gratitude). Results Data from 559 participants were analyzed. Palliative care volunteers had overall significantly higher levels of psychological resources than control groups. Multivariate analysis revealed, among sociodemographic and psychological characteristics that showed differences between groups at the univariate level, the most efficient predictors of group status. The best criteria to distinguish palliative care volunteers from health and social sector volunteers were older age, having received training, and lower levels of self-compassion. To distinguish palliative care volunteers from people with no volunteer activity, older age and non-active professional status were the best criteria. Conclusions Palliative care volunteers displayed more psychological resources than controls. However, older age and being trained for volunteering, emerged as stronger factors for distinguishing palliative care volunteers from controls. Pursuing research about these volunteers should facilitate recruitment, training, and retention.