Efficient use of energy is an essential aspect of green building development. In order to achieve a more energy efficient society, innovation of solar photovoltaic (PV) technologies is a necessity. Collaboration between innovators is regarded as important for innovation; however, the existing literature has made few attempts to investigate how a collaboration network can affect technology innovation in the context of the solar PV sector. This study aims to fill this research gap. In this study, innovation activities are categorized as exploratory innovation and exploitative innovation. A conceptual framework and a series of hypotheses are proposed from the perspectives of network structure (including direct ties, indirect ties, and network efficiency) and network composition (such as geographical proximity, institutional proximity, and technological proximity). The empirical results show that in the solar PV sector of China, collaboration networks with different kinds of structure and composition can imply diverse effects on exploratory innovation and exploitative innovation. Followed with the derived results, it can be concluded that network collaboration is not always beneficial for PV technology innovation. The research findings could convey useful information to both practitioners and policy-makers to adopt appropriate strategies for promoting effective innovation collaboration.