In order to research on the law of methane released through the pore in coal particles, the methane desorption experiments were conducted, respectively, on four types of particle size of coal samples under three different initial adsorption pressures. The cumulative methane desorption quantity (CMDQ) with time increasing was obtained to show that the reciprocal of CMDQ was in linear relation with the reciprocal of the square root of time, and the correlation coefficients were all above 0.99, on basis of which an empirical formula of CMDQ was established. Then, according to Fick diffusion law and Darcy percolation law, the mathematical models of methane emission from the spherical coal particles were created, respectively, and the corresponding calculating software was programmed by the finite difference method to obtain the simulated CMDQ of each sample under different conditions. The methane emission rate functions (MERF) of the simulation and the experiment were also calculated, respectively. Comparative analysis between the numerically simulated outcomes and the assay results reveals that the simulation outcomes as per Darcy’s law match the experimental data better, while the simulated results by Fick’s law deviate greatly, which indicates that the methane flowing through coal particles is more in accordance with Darcy’s law.