In the context of debates about the implications of asset-based approaches for health inequalities, this thesis considers how volunteering in organised community settings may, or may not, mitigate the detrimental psychological impacts of poverty in people's lives. It contributes to the development of theoretical understandings of how experiences of volunteering relate to psychological wellbeing in such contexts, through development of a psycho-social perspective. Health inequalities in the UK have not only persisted, but increased in the last decade, and have been exacerbated by the Covid-19 pandemic, while poverty is increasing in prevalence and severity at the time of writing. Psychosocial factors, such as shame, stress, and social isolation have been identified as significant determinants of intersecting dimensions of inequality, including socio-economic status, class, gender and ethnicity. Psychological wellbeing has been identified as key to processes through which asset-based approaches, including volunteering, are proposed to enhance the health of individuals and communities facing the greatest disadvantages. Most of the literature on volunteering and wellbeing is concerned with psychological constructs operating at an individual level, with little focus on the wider social, political and economic contexts in which volunteering takes place. The power relations implicated in analyses of health inequalities have not been considered in relation to volunteer wellbeing. Power relations operate through implicit, unrecognised processes, embedded in our sense of who we are and our place in the social order, manifesting our habitus, while shame is rarely disclosed or even recognised in social interaction, yet may be powerful in shaping our feelings about ourselves. Therefore, this study adopted an ethnographic psycho-social approach, which critically explored narratives and practices of volunteers and organisations, to consider their unspoken and implicit motivations and meanings. This involved participant observation and interviews with eleven volunteers and four voluntary organisation managers, in two different settings. The analysis considers the organisational and societal level contexts, including the significance of denigrating neo-liberal discourses which blame disadvantaged people for their own suffering, and how volunteering may enable people to defend against these. Considering psychological wellbeing through a psycho-social understanding of identity has provided new insight into processes by which volunteers defend against the symbolic violence of denigrating constructions of poor, working-class, and racialised communities and individuals. Volunteers were enabled to enact socially approved values and behaviours, bolstering their self-concept as well as social and cultural capital. Shared narratives of purpose and meaning promoted a sense of collective identity, facilitating a sense of belonging which to mitigated feelings of shame and exclusion associated with their experiences of adversity. However, analysis of the organisational contexts found that their assimilation of discourses of individual responsibility, together with largely unrecognised power dynamics, reinforced volunteers' perceptions of their powerlessness. In one setting a narrative of collective victimhood served to defend against blame but also reinforced feelings of powerlessness and a sense of ressentiment (Hoggett et al., 2013). The findings imply that for asset-based approaches to effectively address health inequalities requires a shift from a dominant focus on individuals, to one of facilitating development of positive collective identities. These may enhance individuals' self-concepts, social support and belonging, but also open possibilities for collective empowerment, to challenge and resist the drivers of inequalities.