We have demonstrated a novel method to enhance TiO₂ photocatalysis by adopting a new ultrathin tetrahedral-amorphous-carbon (ta-C) film coating on Ag nanoparticles to create strong plasmonic near-field enhancement. The result shows that the decomposition rate of methylene blue on the Ag/10 Å ta-C/TiO₂ composite photocatalyst is ten times faster than that on a TiO₂ photocatalyst and three times faster than that on a Ag/TiO₂ photocatalyst. This can be ascribed to the simultaneous realization of two competitive processes: one that excites the surface plasmons (SPs) of the ta-C-film/Ag-nanoparticle hybrid and provides a higher electric field near the ta-C/TiO₂ interface compared to Ag nanoparticles alone, while the other takes advantage of the dense diamond-like ta-C layer to help reduce the transfer of photogenerated electrons from the conduction band of TiO₂ to the metallic surface, since any electron transfer will suppress the excitation of SP modes in the metal nanoparticles.