Technological innovation and industrial structure upgrading have become two strategic initiatives to realize a green economic development in the new development model of China. Exploring the relationship between green economic efficiency and the coupling degree of technological innovation and industrial structure upgrading is essential to achieve the visionary goal of green economic development and socialist modernization. This paper measures the coupling degree of technological innovation and industrial structure upgrading, classifies the coupling types based on the panel data of 30 provinces in China from 2012-2019, and measures the green economic efficiency of 30 provinces in China using the super-efficient model (SBM), based on a spatial econometric model to study the relationship between green economic efficiency and the coupling degree of technological innovation and industrial structure upgrading. The research results show that there is a significant positive effect on green economic efficiency among regions; the coupling degree of technological innovation and industrial structure upgrading has a significant direct effect and a spatial spillover effect on green economic efficiency, the spatial spillover effect plays a major role. The heterogeneity analysis reveals that in the regions with higher development and coordination degrees of technological innovation and industrial structure upgrading, the coupling degree of technological innovation and industrial structure upgrading has a significant effect on the green economic efficiency of the region, and in the regions with lower development and coordination degrees of technological innovation and industrial structure upgrading, the coupling degree of technological innovation and industrial structure upgrading has a significant positive effect on the green economic efficiency of the region and neighboring areas.