Green development is an important component of China’s new development concept. Pilot Free Trade Zones (PFTZs), as “experimental fields” for promoting reform, deepening opening-up, and raising the level of an open economy, are important open areas for China to promote green development. However, existing related research is not extensive. This article takes PFTZs as quasi-natural experiments, with the Yangtze River Economic Belt (YREB) as the research area. Based on urban panel data from 2006 to 2020, using multi-period differences-in-differences and spatial differences-in-differences models, it explores the impact effects of PFTZs on urban green development and their potential mechanisms. The research findings indicate: (1) Overall, PFTZs significantly promote urban green development, with variations in impact effects due to different batches and locations of establishment. (2) Mechanism tests show that PFTZs mainly promote urban green development by stimulating technological innovation, industrial upgrading, and reducing government intervention. (3) From the perspective of spatial spillover effects, the establishment of PFTZs not only promotes the green development process in the host cities but also has a promoting effect on the green development of surrounding cities.