Green innovation efficiency (GIE) determines the division of labor in high-tech industries in regional value chains. Currently, China’s high-tech industries have not yet formed a systematic, balanced, and efficient green innovation network. Hence, to clarify the potential space structure of China’s high-tech innovation activities, this study adopts the super-efficiency SBM model to measure efficiency and uses the improved gravity model and social network analysis method to construct the spatial correlation matrix and process network analysis. The results show that (1) the GIE of high-tech industries in different provinces differs considerably and the spatial distribution is uneven. The mean GIE values in the eastern, central, western, and northeastern regions are characterized by gradient decrease. (2) From 2012 to 2019, no significant change was observed in the GIE spatial correlation intensity of China's high-tech industry. (3) Henan, Shandong, Shaanxi, Guangdong, and Hunan are the important nodes in the correlation network. These provinces have a strong influence on the network and can effectively control the flow of innovative elements. (4) In the correlation network, the interaction within the block is stronger than that between the blocks. Blocks II and IV are the hinterland of Blocks I and III, respectively, providing Blocks I and III with innovative elements. The conclusions of this study provide a theoretical basis for policy makers to promote the efficient and sustainable development of the high-tech industry in China.