A gold nanoparticle-coated and surface-textured TiO2 inverse opal (Au/st-TIO) structure that provides a dramatic improvement of photoelectrochemical hydrogen generation has been fabricated by nano-patterning of TiO2 precursors on TiO2 inverse opal (TIO) and subsequent deposition of gold NPs. The surface-textured TiO2 inverse opal (st-TIO) maximizes the photon trapping effects triggered by the large dimensions of the structure while maintaining the adequate surface area achieved by the small dimensions of the structure. Au NPs are incorporated to further improve photoconversion efficiency in the visible region via surface plasmon resonance. st-TIO and Au/st-TIO exhibit a maximum photocurrent density of ∼0.58 mA cm-2 and ∼0.8 mA cm-2, which is 2.07 and 2.86 times higher than that of bare TIO, respectively, at an applied bias of +0.5 V versus an Ag/AgCl electrode under AM 1.5 G simulated sunlight illumination via a photocatalytic hydrogen generation reaction. The excellent performance of the surface plasmon-enhanced mesoporous st-TIO structure suggests that tailoring the nanostructure to proper dimensions, and thereby obtaining excellent light absorption, can maximize the efficiency of a variety of photoconversion devices. © 2013 The Royal Society of Chemistry.