The pyrolysis of Shenmu coal macerals was performed in TG151 thermobalance. The volatile matter evolved in primary and secondary devolatilization and devolatilization kinetics were studied. The volatile matter evolved during primary devolatilization is the major part of the total volatile matter, especially for vitrinite. The percentage of volatile matter evolved during primary and secondary devolatilization suggested that inertinite have higher thermal stability. Though the heating rate can affect the percentage of volatile matter evolved during primary and secondary devolatilization, the order of volatile matter in all the temperature range is the same: vitrinite > parent coal > inertinite. The kinetic analysis of devolatilization using distributed activation energy model (DAEM) shows that the activation energy existed relatively large error at the conversion of initial 10% and final 10%. And the conversion of 10% to 90% was used to describe the variation of activation energy during pyrolysis. The activation energy of vitrinite appeared a minimum of about 50% conversion, but that of inertinite always increased as pyrolysis went on, indicating the different structure and chemical composition between them. Inertinite has higher activation energy and lower pyrolysis rate than vitrinite.