The mode selectivity of methane dissociation is studied on three different Ni/Pt-bimetallic alloy surfaces using a fully quantum approach based on reaction path Hamiltonian. Dissociative sticking probability depends on the composition of alloying metals, excited vibrational mode, and symmetry of the reaction path about the plane perpendicular to the catalyst surface containing the carbon atom and two hydrogen atoms. Our calculations show that symmetry of the minimum energy reaction path depends on the surface alloy composition. In the transition state, the dissociating C–H bond elongates significantly for the dissociation of methane on these alloy systems. A significant decrease in the frequency of the symmetric stretching mode and the two bending modes near the transition state is observed on all the alloy surfaces. Under the vibrational adiabatic limit, excitation of these softened modes enhanced the dissociation probability compared to the ground vibrational state. The reaction probability values decrease abruptly at the incident energies less than the zero-point energy corrected barrier height. With the inclusion of non-adiabatic vibrational coupling terms, reaction probability in the low incident energy region increases to a greater extent, and mode selective behavior also becomes different from that observed within the vibrational adiabatic limit. Symmetric stretching mode displayed the highest reactivity on all the alloy surfaces. Overall, Ni8/Pt(111) is found to be the most reactive toward the methane dissociation.