In recent years, with the increasingly serious problems of air pollution, climate change, and environmental damage, the proposal of green finance has a great impact on the environment. The country has issued a series of green finance policies to guide the allocation of resources, fully leverage the functions of the financial market, and increase the investment of green credit. This study collects relevant data on green finance and export trade structure, analyzes the correlation between the two in different provinces from 2001 to 2020, and constructs gray correlation models, fixed effects models, and random effects models. The results indicated that there was a significant difference between the maximum and minimum values in optimizing the export trade structure. The average value was relatively low, indicating that the export trade situation in different regions varies greatly and there is an imbalance in development. Green finance's maximum and minimum values were relatively small, and the average reached 0.4908. The coefficient of green finance in optimizing that structure was 0.263, which was significantly positive at the 1% level. Every 1% increase in green finance would promote a 0.263% change in the structure optimization. The data show that green finance is developing well in various regions, but there is still a need to increase development efforts. This study indicates that green finance significantly influences the export trade structure. After constructing the green finance reform and innovation pilot zone, green finance can better promote optimizing its regional export trade structure. Although this study focuses on China's green finance and trade structure optimization, its methods and results are equally applicable to countries with similar characteristics in terms of economic development stage, environmental conditions, government support, financial markets, and data availability. The findings of this study can serve as a point of reference and inspiration for the formulation of effective green finance policies in other countries.