BiVO4, an excellent photocatalyst for oxygen production, has been studied extensively. Many attempts have been made to change the conduction band of BiVO4 to satisfy the H2O/H-2 potential. In this paper, yttrium is introduced to adjust the energy band structure of BiVO4. A novel BiVO4:YVO4 solid solution with a new dodecahedron shape exposing two facets, {101} and {100}, is successfully prepared. On doping with Y, the crystal system of BiVO4 changes from monoclinic to tetragonal. The improved symmetry of the crystal system makes the (100) and (010) of {100} facets entirely identical, resulting in dodecahedron tetragonal BixY1-xVO4. The energy levels of the two facets show slight nonconformity. So the photogenerated electrons and holes can be separated efficiently between the adjacent exposed facets to produce H-2 and O-2, respectively. Through the study of photocatalytic performance, BixY1-xVO4 with Pt as co-catalyst shows highly efficient photocatalytic activity and can split pure water at the stoichiometric ratio. (C) 2017 Elsevier Inc. All rights reserved.