The photovoltaic (PV) industry in China is still in the early stage of development and is extremely unbalanced; breakthroughs in key technologies are necessary. To achieve high efficiency and sustainable development, it is important to identify the bottleneck of the whole industry chain through the analysis of overall industrial technical efficiency. Based on the current situation of the PV industry, this study builds the data envelopment analysis (DEA) model to respectively evaluate the efficiency of PV devices and power generation in the PV industrial chain. The Tobit model is used to conduct an empirical analysis of the factors affecting the efficiency of the PV industry. The results show that the industrial efficiency of PV devices is at a medium level and that it is necessary to strengthen regulation and awareness at the industrial scale. However, the PV power generation industry as a whole is at a low efficiency level, especially the inadequate technical level, which has a negative impact on the improvement of industrial efficiency. Finally, countermeasures and suggestions at the enterprise and government level are put forward to improve the efficiency of the PV industry in China.