In today’s world, green development has become an important trend, and many countries regard the development of green industry as an important measure to promote economic restructuring. Green development is consistent with sustainable development in ideology. China’s economy is in the stage of high-quality development. As an important foundation for China’s external economic development, the free trade zone can play a good role in promoting its green and high-quality development. Based on the data of 18 free trade zones in China in 2020, this paper explores the green and high-quality development path of the China Pilot Free Trade Zone. Firstly, the green development index is constructed according to the existing research and experience, and then the fuzzy set qualitative comparative analysis method is used to evaluate the green and high-quality development path. The results show that the development of pilot free trade zones is not the result of a single condition but the result of a combination of green policy effectiveness, foreign investment participation, green production growth rate, and other conditions. Combined with the green and high-quality development path, this paper further provides enlightenment for the development of the China Pilot Free Trade Zone.