Global environmental governance (GEG) is widely recognized as particularly networked. And negotiation sites are sites not only of formal decision-making processes but also of intense networking by various actors. Use of formal social network analysis to analyze both networked governance and governance networks in global environmental politics has to date mostly rested on relatively easy-to-get data, such as membership in formal organizations or treaties. These analyses give useful broad-brush analyses to help think about the social structure of environmental governance, but relatively limited inferences can be drawn about key processes that network analysis can help understand, such as learning, diffusion, and other forms of institutional interaction. This article proposes how to advance the value of the method in the field by focusing on the personal networks of actors who make up the decision-making processes in GEG. Negotiation sites could thus become important sites for collection of data about these networks, through direct observation of interactions, intensive short interviews, and surveys, in particular.