This interpretive case study explored workplace and networked epistemologies of social learning enabled by the establishment of Regional Centres of Expertise (RCE) in Southern Africa. By offering deeper insights into the networking and sharing in these communities, the study makes the case that these are emerging communities of practice in Education for Sustainable Development (ESD). The case study used qualitative methodology by means of a mixed methods approach of document analysis and in-depth interviews with key RCEs informants from RCE Makana and RCE KwaZulu-Natal. The conceptual framework is represented as theoretical perspectives from current adult education that focus on professional disciplines including multidisciplinary / inter-professional perspectives, those that focus on communities of practice, and those that focus on the workplace learning. The study opens up deeper understandings of socio-cultural and structural features in the two nested cases. It provides insights into RCEs that can be both enabling and constraining of agency.