The role of technological innovation (TI) in green development is controversial. Based on 2003–2017 panel data of 108 cities in the Yangtze River Economic Belt (YREB), this study constructed an index system to evaluate urban green development and analyzed the role of TI on urban green development with the help of a panel econometric model. The results show that: (1) From 2003 to 2017, the levels of TI and green development of cities in the YREB have gradually improved, but the core–periphery structure is obvious, and the levels of TI and green development in the lower reaches are significantly higher than those in the middle and upper reaches. (2) TI has a significant positive role in promoting green development, showing a U-shaped nonlinear relationship, and this relationship varies from region to region. (3) TI has a significant impact on green development with direct and indirect effects. In the economic and social dimensions, TI has a positive impact on green development, while in the ecological dimension, the direct effect and indirect effect have opposite relationships. (4) TI has a significant threshold effect on green development, and there are differences in threshold characteristics between the three dimensions. These findings provide a scientific basis for policymaking about innovation-driven regional green development, and it can enrich the related theories of environmental economic geography.