The crystal structures, band structures, density of states and chemical bonding for NaBiO3 photocatalyst were performed using first principles method. The results indicated that NaBiO3 has an indirect band gap of about 2.20 eV. The calculated positions of valence bands maximum and conduction bands minimum show that NaBiO3 has strong oxidation and reduction ability to decompose organic contaminants and split water to hydrogen under visible light irradiation. The distortion of BiO6 octahedra and the lighter effective mass of carriers facilitate the separation and migration of electronic and hole pairs and improve photocatalytic performance. (C) 2013 Elsevier B.V. All rights reserved.