The superfine pulverized coal has a greater potential for reducing NO, emissions in the staged and oxyfuel combustion technologies. The compositions and evolving processes of the volatile species during coal pyrolysis are important for understanding the pyrolysis mechanisms and pollution control strategies. In spite of numerous works focused on the description of coal thermal decomposition, the mechanism of formation reactions for particular gaseous products of coal pyrolysis like CH4 remains unclear. In this paper, the mechanisms of CH4 formation during superfine pulverized coal pyrolysis in N-2 and CO2 atmospheres are investigated under non-isothermal conditions in a fixed-bed reactor. The effects of coal type, particle size and temperature on the evolved CH4 and its formation mechanisms are analyzed. In addition, the total overlapped CH4 evolution curves are resolved applying the deconvolution method through numerical analysis. Five constituent reaction complexes induced by different functional groups are recognized. Five CH4 precursors involving in the CH4 revolution during coal pyrolysis are confirmed, applying the solid-state C-13 NMR analysis. Different CH4 formation mechanisms initiated from the thermal decomposition of the functionalities are concluded, with the products competing for the donatable hydrogen for stabilization. (C) 2014 Elsevier Ltd. All rights reserved.