The utilization of photovoltaic power generation represents a pivotal strategy for the transition of traditional energy systems towards decarbonization, and is of paramount importance in achieving global climate goals. A social network analysis was employed to examine the evolutionary characteristics of the global PV power generation trade network, based on the trade data of global photovoltaic devices from 2012 to 2021. The analysis aims to elucidate the basic situation and development trend of this network. It was found that during the period from 2012 to 2021, the global PV power generation trade network underwent substantial development and expansion, with trade links between countries becoming increasingly close. The trade network is distinguished by high aggregation and short path lengths, exhibiting pronounced “small-world” characteristics. The nodes of the global PV power generation trade network exhibit a stable “core-edge” structure. Concurrently, China’s central position is becoming increasingly evident, and its pivotal role in the global PV power generation trade network is intensifying. This has positioned China as a pivotal force in the advancement of trade in this field, with the center of gravity of trade activities demonstrating a tendency towards an eastward ascendance and a westward decline.