This paper presents the first observation of the broad-range NIR DRIFT spectrum of CH4 adsorbed on HM zeolite including different combinations of C-H bending and stretching vibrations and overtones of those vibrations. The obtained results indicate that adsorption of methane results in the strongest perturbation of the combinations of v(2) and v(4). C-H bending frequencies with each other and with the v(3) asymmetric stretching frequency. Therefore, it is suggested that those combinations could be used as a better index of methane perturbation and of the reaction coordinate of methane protolytic dehydrogenation than the fundamental frequencies commonly used for this purpose.