Although the literature has studied the direction and extent of the effect of green finance on industrial-structure optimization, quantitative analysis of the coupling coordination and spatial–temporal differences between green finance and industrial structure is relatively scarce. Therefore, in this paper, we built the theoretical framework of the coupling coordination relationship between green finance and industrial-structure optimization, and then we used the coupling coordination degree and geographic detector model to investigate the spatial–temporal evolution characteristics and influencing factors of the coupling coordination between the two based on the panel data of 31 provinces from 2012 to 2019. The results show that China’s green finance and industrial-structure optimization have basically reached the primary coupling, and the coupling coordination degree is from 0.40 to 0.43, which shows a “W”-type fluctuation trend of recovery. The regional gap of the coupling coordination degree firstly decreased and then increased, showing a change law of “agglomeration, equilibrium and agglomeration”. In the spatial dimension, the high-level coordination region showed an increasing trend of “fragmentation” fluctuation, while the low-level coordination region concentrated in the central and western regions with a tendency of “low value locking”. The trend surface showed a spatial characteristic of “high in the north and low in the south–high in the east and west and low in the middle”. We also found that the dependence of foreign trade and technological innovation are the main factors affecting the coupling coordination degree, and the interaction between government support and human capital synergistic is the crucial channel for the coevolution of green finance and industrial structure to promote green and low-carbon development.