Rhodium-doped barium titanate (BaTiO3:Rh) powder was prepared by the polymerized complex (PC) method, and the photocatalytic activity for H2 evolution from water was examined. BaTiO3 is a wide-gap n-type semiconductor having a band gap of 3.0 eV. Doping Rh species into the lattice of BaTiO3 resulted in the formation of new absorption bands in visible light region. Upon visible light (λ > 420 nm), BaTiO3:Rh modified with nanoparticulate Pt as a water reduction promoter was capable of producing H2 from water containing an electron donor such as methanol and iodide. The best material prepared by the PC method exhibited higher activity than that made by a conventional solid-state reaction method. Visible-light-driven Z-scheme water splitting was also accomplished using Pt/BaTiO3:Rh as a building block for H2 evolution in combination with PtOx-loaded WO3 as an O2 evolution photocatalyst in the presence of an IO3(-)/I(-) shuttle redox mediator. Photoelectrochemical analysis indicated that a porous BaTiO3:Rh electrode exhibited cathodic photoresponse due to water reduction in a neutral aqueous Na2SO4 solution upon visible light.