Abstract: It is a great challenge for the selective hydrogenation of phenylacetylene to styrene over non-noble metal catalyst under mild reaction conditions. Carbon-modified TiO₂ supported nickel nanoparticles catalyst was prepared using impregnation-reduction method, which exhibited excellent photocatalytic performance in selective hydrogenation of phenylacetylene under visible light irradiation. The photo-excited hot electrons over Ni nanoparticles promoted the activation of reactants. The electron-rich Ni nanoparticles inhibited the adsorption of phenylethylene on the surface of Ni/TiO₂, which increased the selectivity of phenylethylene. This work provides an environmentally-benign and efficient method for photocatalytic hydrogenation of phenylacetylene.