With the increasing consumption of fossil energy and changes in the ecological environment, meeting the energy demands required for industrial and economic development with clean and efficient power generation is a major challenge of our society. Solar energy is considered to be one of the most renewable and sustainable energy sources, and photovoltaic power generation has become an important research topic. This study combines data envelopment analysis (DEA) with Tobit regression analysis to assess the efficiency of photovoltaic power generation in China and analyze factors affecting efficiency to improve the efficiency of photovoltaic power generation. The results show that there are obvious regional differences in photovoltaic power generation efficiency in China. The phenomenon of focusing on economic development at the expense of the use of solar power generation still exists. The establishment of photovoltaic demonstration projects, the implementation of differential electricity price policies, and the promotion of photovoltaic precision poverty alleviation can alleviate economic pressure and effectively improve the efficiency of photovoltaic power generation.