This paper carries out an analysis of the formation and transformation of social relations and networks of access to resources in the professional trajectory of micro-entrepreneurs operating in an urban informal African economy. The analysis of social networks is rooted in Granovetter’s structural embeddedness framework combined with the dynamic and discursive conception of social relations of Harisson White (embeddedness and decoupling). Life stories of micro and small entrepreneurs in Bobo-Dioulasso (Burkina-Faso) are analyzed by mixing qualitative and quantitative methods. Results suggest that the construction of social networks and interpersonal relations of access to resources is a long-term process. A co-construction of social networks and economic activity is observed; it challenges the argument that social capital is a substitute for a lack of personal resources. The growth of small and micro activities is linked to the professionalization and stabilization of a social network, and even to the institutionalization of access to resources.