We investigated photophysical and photooxidation properties of NaBiO3 containing Bi (V) for the first time. The optical absorption of NaBiO3 was characterized by the sharp decrease at about 470 nm followed by the long tail up to 600 nm. The photooxidation activity evaluated from the decomposition of gaseous 2-propanol and methylene blue (MB) dye in the liquid phase revealed that NaBiO3 is a prominent material for photooxidation of organics in the range of visible light. In addition, we calculated the electronic structures of bulk NaBiO3 in the framework of density functional theory (DFT). As a result, strong dispersion from the hybridized Na 3s and O 2p orbitals that was identified at the bottom of the conduction band (CB) was considered to contribute to the high activity of this material.