This paper represents a research response to the current vision on transformations regarding the capacity building of smart cities focused towards sustainability, by addressing the knowledge based urban development and collaborative tools that support the development, dissemination, and use of knowledge. The purpose of this paper is to develop a collaborative pattern of knowledge networking, focusing on sustainability goals within a smart city concept, using the logic of the Complex Adaptive System (CAS). The study was carried out in an innovation cluster in Romania; the Social Network Analysis (SNA) was used as a tool to perform the study. The results of this analysis, due to the suggested networking, have led to delimitation of the roles that Groups of Competences play to enhance the sustainability of smart cities in areas where the use of knowledge has the greatest impact. Results show that the success of the smart solutions’ implementation depends on how the social and competence structures of the network are shaped and whether it permanently adapts to fit the sustainability objectives in the considered areas.