Innovations of organizations are doubly embedded in knowledge networks constituted by coupling among knowledge elements and in social networks formed by collaborative relationships among organizations. This study explores the structural properties of such relationships and their possible influences on organizational innovations in terms of exploitation and exploration in the emerging nano-energy field. Results indicate that the knowledge networks and the technology-based collaboration networks in the nano-energy field are decoupled and that they have different degrees of integration. Some structural features of knowledge and collaboration networks influence organizations’ exploitative and exploratory innovations in diverse ways. Firstly, direct ties of an organization's knowledge elements in a knowledge network have an inverted U-shaped effect on its exploitative innovation, which is not the case in exploratory innovation. Direct ties in a collaboration network have an inverted U-shaped effect on both its exploitative and exploratory innovations. Secondly, indirect ties of an organization's knowledge elements in a knowledge network affect its exploitative innovation, but not its exploratory innovation. However, indirect ties in a collaboration network affect exploratory innovation, but not exploitative innovation. Thirdly, non-redundancy among ties in a knowledge network exhibits the opposite effect, hindering exploitative innovation, but favoring exploratory innovation. By contrast, non-redundancy among ties in a collaboration network favors exploitative innovation, but shows a non-significant effect on exploratory innovation.