There is a rising global concern about mercury use in small-scale gold mining because of its harmful effects on ecosystems and human health. Associative entrepreneurship has been promoted as a way of accessing alternative techniques to address this concern. By associative entrepreneurship, in this paper we mean the creation of local associations between small-scale gold miners in order to acquire more environmentally-friendly technologies. We built a behavioral simulation model to assess the feasibility of associative entrepreneurship in the context of the public-good dilemma that gold mining communities face. The model construction is based on results from field economic experiments, and properly replicates the observed behavioral patterns; thus, it reveals that sustained collective action is possible when miners completely understand the social dilemma they face, but that self-organization is not possible. Features such as reciprocity and temptation to free ride partially explain why self-organization fails. In such a case, external intervention has a key role in promoting programs that improve the understanding of the social dilemma faced by artisanal and small-scale gold miners.