Green low-carbon development is the direction for coal enterprises to cope with overcapacity, industrial restructuring and enterprise transformation. Based on the connotation of green low-carbon development, this paper deconstructed the green low-carbon development of coal enterprises into a process of coupling and coordinated development of green low-carbon system (GLCS) and innovation development system (IDS) from a systematic perspective, further deconstructed the green low-carbon system into two subsystems of environment (ES) and resources(RS), and deconstructed the innovation development system into two subsystems of innovation (IS) and growth(GS), built the coupling and coordination evaluation model and grey relational degree model of green low-carbon development of coal enterprises, and made an empirical analysis of China Shenhua Energy Company Limited ("CSEC") and China National Coal Group Corp (“CNCGC”) in 2010-2017. The empirical analysis showed that the coupling and coordinating level of GLCS and IDS of CSEC and CNCGC is both not high, but there are differences in evolutionary trends and causes, and the coupling and interaction mechanism needs to be strengthened; the coupling coordination degree between ES and IS is good, and between RS and GS is the worst in CSEC, and the coupling coordination degree between RS and GS is highly correlated with the coupling coordination degree between GLS and IDS, and improving the level of IS is an important direction for CSEC; But in CNCGC the coupling coordination degree between subsystems fluctuates greatly, and there is no persistent good and persistent bad coupling, but in the past two years, the level of coupling coordination among subsystems has a rising trend, and the level of RS and the degree of coupling coordination between ES and IS have the highest correlation with the degree of coupling coordination between GLS and IDS. Coal enterprises should improve the interaction mechanism among subsystems, strengthen the driving role of green innovation, and promote green low-carbon development.