Highway construction reduces the production costs of enterprises, which is conducive to their increased investment in environmental management and the adoption of green production technologies, thereby promoting regional green economic growth. Traditional research mainly focuses on the pollution problem in the transportation infrastructure and transportation process, and it is difficult to explain the spatial spillover problem of the green economy brought by transportation. We measured the shortest passage time and market access of the Yangtze River Economic Belt highway from 2005 to 2019. Meanwhile, we measured the green total factor productivity based on the Malmquist-Luenberger index. The empirical results show that highway construction has a significant role in promoting green economic growth in the Yangtze River Economic Belt. However, there is obvious regional heterogeneity in the degree of effect. Market access has the largest effect in large cities, followed by medium cities, and has the smallest effect on small cities. This suggests that there is an environmental “bottoming-out effect” in highway-induced industrial transfer. Further, we find that green technology innovation is the mechanism by which highways affect green economic growth.