We report a combined experimental and theoretical study comparing methane dissociation on three different platinum surfaces Pt(111), Pt(211), and Pt(110)-(1 × 2). Reflection absorption infrared spectroscopy (RAIRS) was used to detect chemisorbed methyl species formed by dissociative chemisorption of CH4 on specific surface sites and to measure surface-site-specific sticking coefficients of CH4 on the terrace, step, and ridge sites as function of incident translational energy. Methane dissociation is observed to be direct on all sites and diffusion of the chemisorbed methyl species is absent for surface temperature below 150 K. The experimental data are compared with the results of density functional (DFT) calculations that give minimum energy barriers for CH4 chemisorption that properly account for the experimental relative site-specific reactivities. Also in agreement with experiments, DFT results predict a negligible effect of co-adsorbed H and CH3 species on the vibrational frequency of a methyl group chemisorbed on terrace and step sites of Pt(211). However, the origin of the red-shift of the RAIRS peak of CH3 chemisorbed on terrace sites compared with that on step sites of Pt(211) remains elusive and still demands further investigation.