There is a lack of empirical research around sub‐national Social Investment programs, and a lack of connectivity with social innovation. This paper addresses these gaps by drawing on twenty individual case study evaluations, conducted across ten EU member states as part of a larger Horizon 2020 project (Innovative Social Investment: Strengthening communities in Europe, grant agreement number: 649189). It does so through a “governance of activation” lens. We find that volunteering was a significant feature of many of the cases we researched, as both a means of funding Social Investment, and a means by which activation (through the development of human and social capital) might be achieved. Yet volunteering is a gap in the theoretical literature around Social Investment, and one that needs to be addressed. We also find that examining Social Investment at the local level provides a much more nuanced and complex picture than nationally focused extant research.