The presence of Ag+ ions enhanced the photodegradation activity of BiVO4. Photoreduction of Ag deposited on the BiVO4 surface was obtained. Luminescence and electrochemical results elucidated the photocatalytic mechanism. Holes and oxygen radicals were the main reactive species generated by BiVO4/Ag+. Used BiVO4/Ag+ exhibited photocatalytic antibacterial activity toward E. coli.