In the UK context of financial austerity and the promotion of the social responsibility through the concept of the “Big Society,” volunteers are becoming a more important part of the labor workforce. This is particularly so in the long-term care (LTC) sector, where both shortages of staff and demands for support are particularly high. This article investigate the levels and profile of contribution of volunteers in the LTC sector using a large national data set, National Minimum Data Set for Social Care, linked to local area levels of rurality and socio-economic status. The analysis shows that volunteer activity in formal care services varies between sectors and service types, with no strong relationship between local area deprivation, unemployment levels, and levels of volunteering. However, some significant association was found with level of rurality. The contribution of volunteers is most evident in provision of counseling, support, advocacy, and advice.