For a long time, volunteers and their voluntary actions have been more or less neglected by the society and scholars. With the diversification of social governance actors and the deep involvement of volunteers in social governance, the existence and role of volunteers in the public sphere is becoming increasingly indispensable. It means that volunteers and their voluntary actions provide new ideas for seeking to solve the dilemma of “governance failure” and “reform failure”. In this process, no matter whether the volunteers are motivated by free will or by benefit, the government and society should treat them as benefit seeking in order to improve the positive role of volunteers in social governance. Accordingly, volunteers tend to be organized while participating in social governance in order to achieve the sustainability of voluntary actions. Therefore, how to organize and accept volunteers and their service into the social governance system, as a significant element of cooperative governance construction, should become an important issue and feasible approach for the practical innovation of social governance and theoretical construction of cooperative governance.