China has successively set goals of carbon peaking and carbon neutrality, aiming to transform to a green and low-carbon economy. Collaborative environmental governance (CEG) is an important way to achieve this transformation. To improve collaborative environmental governance, the study of the evolution of the collaborative environmental governance network (CEGN) is necessary. In this study, the CEGNs in different periods in Guizhou Province, China are established based on social network analysis. Then, the evolution of environment governance policy implementers’ functions in the network is investigated by two-dimensional (breadth and intensity) matrices. Moreover, the evolution of core implementers’ functions and its impacts on the operation of the network are analyzed based on the network stability. The results show that the network size, frequency of collaboration, and cohesion have gradually increased, and the network structure has changed from a loose pattern to an expanded and balanced system. Implementers such as the governments of municipalities (prefectures) (MGs) and counties (districts) (CGs), urban management committee (UMCs), and municipal (prefecture) ecological environment bureaus (MBEEs) have played leading and coordinating roles at different phases. However, the cohesion of the network is low, indicating a low level of collaboration. This study integrates the collaborative governance theory and social network analysis, which provides a new way for the study of CEG. In addition, the CEG effect is evaluated by analyzing the evolution of the CEGN, which provides a reference for the CEG policy making in developing regions.