Population migration continues to reshape the spatial pattern of China’s population and regional economic development. During this internal migration process, production and consumption patterns often change, ultimately leading to changes in green total factor productivity. This paper, based on the Chinese population census data and 1% sampling survey data from 2005 to 2015, utilizes social network analysis methods to measure the labor mobility network indicators of 284 prefecture-level cities. Further, this paper analyzes the impact and mechanisms of regional network status on green total factor productivity using a panel fixed effects model. We find that as network density increases, the interpersonal connections between regions become closer, and the network exhibits a clear pattern of “concentrated inflows” and “dispersed outflows”, with the trend of forming strong alliances becoming increasingly apparent. Regions positioned centrally either in terms of network in-degree or out-degree exhibit higher green total factor productivity. Among these, the labor mobility network plays a crucial role in enhancing green total factor productivity through the channel of technology diffusion effects, which improve investment efficiency via knowledge exchange and material capital accumulation. The promotive effect of labor network status on green total factor productivity is more pronounced in the eastern regions, where talent quality is higher, and in areas with fewer restrictions from the household registration system.