A relatively less explored plasmonic material, Pd, on the TiO2 interface has been utilized to boost the catalytic efficiency of rutile TiO2 as a photoelectrocatalyst material. To obtain desired plasmonic behavior, Pd ions deposited over TiO2 were reduced under cold/nonthermal hydrogen plasma, for complete reduction of as-deposited Pd ions to metallic Pd nanoparticles. The Pd@TiO2 photocatalyst, thus prepared, was then extensively characterized. We emphasize that this particular catalyst can be used as a photoelectrocatalyst, as this is found to exhibit promising photoelectrochemical behavior and its ability as a water oxidation catalyst in water splitting devices. The enhanced catalytic activity achieved by using Pd nanoparticles and subsequent cold hydrogen plasma treatment of Pd@TiO2 is expected to make such a system useful for many other electrocatalytic and related applications.