Combinatorial computational chemistry based on the first-principles approach was applied to the metal sulfide catalysts and studied the dependency of the metal species in the metal sulfide catalysts to the CO hydrogenation process and its products on the electronic level. The dependence of the metal species in the metal sulfide catalysts to the products of the CO hydrogenation process was clarified. This result agreed well with the experimental findings of Koizumi et al. The Pd sulfide catalyst had the highest selectivity of the methanol from the CO hydrogenation process and the catalysts that realized the bride-site adsorption of the CO molecule had the high selectivity of the methanol. The combinatorial computational chemistry approach was effective and useful in designing new catalysts with high activity and selectivity.