Bi/BiVO 4 /V 2 O 5 has been successfully synthesized by a simple annealing of BiVO 4 in Ar/H 2 . The obtained Bi/BiVO 4 /V 2 O 5 was characterized by X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The photocatalytic activities are examined by an oxygen-evolution reaction. When BiO/BiVO 4 /V 2 O 5 in air and Bi 2 VO 5.5 / BiVO 4 /V 2 O 5 in vacuum were compared with the products annealing in other atmospheres, Bi/BiVO 4 /V 2 O 5 exhibited the best performance (2413 μmol•g −1 •h −1 ), which could be attributed to the synergistic combination of Bi, BiVO 4 , and V 2 O 5 . This study may open up a new avenue for the development of an efficient composite photocatalyst.