Titania-on-gold "inverse" nanocomposites were formed by loading smaller TiO2 nanoparticles onto bigger gold nanospheres by combining seed-mediated method with solvothermal method. This new nanoarchitecture exhibits excellent properties in hydrogen evolution from water splitting under visible-light irradiation. The enhanced performance was attributive to the synergistic effect between ultrafine TiO2 nanoparticle and localized surface plasmon resonance effect of gold nanoparticles, which induce the faster separation of photo-generated electrons from Au nanospheres to TiO2 nanoparticle. Besides, the nanocomposites have a strong absorption at around 550 nm, corresponding to the maximum irradiation intensity of solar spectrum. Owing to these outstanding properties, the as-obtained titania-on-gold nanoarchitectures showed promising and great potential for practical applications in photocatalytic field.