This study explored the respective importance of compositional (individual) and contextual (neighbourhood) factors associated with the propensity to engage in formal volunteering among a nationally representative sample of adults in Wales, UK. To date, while certain contextual characteristics of local communities have been found to be associated with the propensity to volunteer, compositional characteristics of residents tend to be stronger predictors. Few studies to date have specifically explored associations with local volunteering opportunities. To address such gaps, this study examined the extent to which such opportunities and broader neighbourhood factors such as urban/rural status and deprivation impacted upon propensities to volunteer, adjusting for important compositional predictors of voluntarism. In summary, while volunteering was marginally associated with a measure of local voluntary opportunities, hinting that the odds of formal volunteering are greater among those living in areas with more local voluntary organizations, this association was not retained following adjustment for other factors. This suggests that much of the area-level variance is explained by spatial variations in compositional factors. Further research is needed to examine determinants of volunteering behaviour at a range of spatial scales by drawing on wider measures of volunteering opportunities, before the factors at play can be fully understood.