We consider the pilot zones for green finance reform and innovation (PZGFRI) set up in 2017 as a quasi-natural experiment, and we adopt the synthetic control method (SCM) to evaluate the possible policy effects of the PZGFRI on the energy consumption structure (ECS) based on panel data from 30 provincial-level administrative regions from 2013 to 2019. The empirical results reveal that the PZGFRI set-up plays a key role in influencing the ECS. The PZGFRI policy significantly optimizes the ECS in both Zhejiang and Guizhou Provinces, with the investigative result in Guizhou Province being better than that in Zhejiang Province. Meanwhile, ranking, placebo, and robustness tests were still valid. This study contributes to a better understanding of the effectiveness of China’s PZGGRI policy on the ECS.