Photovoltaic (PV) industry is a strategic emerging industry in China, which provides risk resistance and autonomy for energy security by its technology innovation structure. The article conducts a comparative study on the technological innovation of PV industry between China and major PV powers to master the technological innovation structure of China’s PV industry. For this purpose, the article analyzes the relative evolution of the data above and profiles the structure of PV industry technological innovation by employing the social network analysis (SNA). Multiple linear regression was applied to analyze driving factors of the PV industry and its mechanism. The results show that: (i) Compared with other major economies, China’s PV industry is characterized by hysteresis, rapid advancement, and industry chain bias towards the midstream and downstream. (ii) The connection of the whole technological network gradually tends to be direct and diversified, but the tightness of the integral connection is decreasing. (iii) China’s siliceous resource retention is the biggest driving force for the development of PV industry, followed by the investment intensity of research and developement (R&D) in the corresponding industry. Based on the above findings, the article puts forward countermeasure recommendations.