DFT simulations have uncovered the origin of the highly selective character of gold nanoparticles in hydrogenation of triple bonds. This is ascribed to the better adsorption of CC at the edges of Au nanoparticles compared with CC. Since the barriers for hydrogenation of triple and double bonds on gold are comparable, selectivity is determined by the binding energy of the reactants. The situation is less favorable over palladium (commercial hydrorefining catalyst), because both CC and CC bonds are adsorbed on the Pd surface. The outcome of the simulations was demonstrated experimentally in mixtures with both propyne and propylene over a Au/CeO₂ catalyst, where C₃H₆ selectivities up to 95% were attained. Our finding opens a new path for chemoselective hydrogenation of molecules containing -yne and -ene groups on gold, with prospective application in petrochemical operations and in the fine chemical industry.