Na0.5Bi0.5TiO3 (BG 3.1 eV) with a valence band formed by Bi(iii) was found as a new photocatalyst for solar water splitting. The water splitting activity of highly crystalline Na0.5Bi0.5TiO3 synthesized by a flux method was much higher than that of the samples synthesized by a solid-state reaction. The optimized RhCr2Ox(0.1 mol%)/Na0.5Bi0.5TiO3/CoOOH(0.02 mol%) gave a 5.1% apparent quantum yield at 350 nm and split water even under simulated sunlight irradiation with a 0.05% solar to hydrogen energy conversion efficiency. We have successfully achieved solar water splitting using a one-step photoexcitation type photocatalyst valence-band-controlled with Bi(iii).