The dissociative chemisorption of CH4 on Pt(111) was studied using quantum state-resolved methods at a surface temperature (Ts) of 150 K where the nascent reaction products CH3(ads) and H(ads) are stable and accumulate on the surface. Most previous experimental studies of methane chemisorption on transition metal surfaces report only the initial sticking coefficients S0 on a clean surface. Reflection absorption infrared spectroscopy (RAIRS), used here for state resolved reactivity measurements, enables us to monitor the CH3(ads) uptake during molecular beam deposition as a function of incident translational energy (Et) and vibrational state (n3 anti-symmetric C–H stretch of CH4) to obtain the initial sticking probability S0, the coverage dependence of the sticking probability S(y) and the CH3(ads) saturation coverage ysat. We observe that both S0 and ysat increase with increasing Et as well as upon n3 excitation of the incident CH4 which indicates a coverage dependent dissociation barrier height for the dissociation of CH4 on Pt(111) at low surface temperature. This interpretation is supported by density functional calculations of barrier heights for dissociation, using large supercells containing one or more H and/or methyl adsorbates. We find a significant increase in the activation energies with coverage. These energies are used to construct simple models that reasonably reproduce the uptake data and the observed saturation coverages.