The adsorption and dissociative reaction of methanol on B 12 N 12 fullerene-like nanocage is investigated by using density functional calculations. Equilibrium geometries, adsorption energies, and electronic properties of CH 3 OH adsorption on the surface of the B 12 N 12 were identified. The calculated adsorption energies range from −1.3 to −34.9kcal/mol. It is found that the electrical conductivity of the nanocage can be modified upon the adsorption of CH 3 OH. The mechanism of methanol decomposition via CO and OH bond scissions is also studied. The results indicate that OH bond scission is the most favorable pathway on the B 12 N 12 surface.