Dendritic-like BiVO4:Ag heterostructure was formed in the process of visible light-irradiated photocatalysis using dendritic-like BiVO4 as photocatalyst, AgNO3 as additive and photocatalytic degradation of Rhodamine B (RhB) solution as model reaction. In the coexistence of BiVO4 and AgNO3, Ag islands (nanoparticles) could be formed on the surface of dendritic-like BiVO4 crystals after Ag+ ions captured the photo-generated electrons, and hence the BiVO4:Ag heterostructure was obtained. The formation of Ag islands can be directly confirmed by TEM technique. The synergistic effect of the formation of BiVO4:Ag heterostructure and Ag+ ions as electron capture agent leads to prominent improvement of the photocatalytic activity, i.e., the decolor efficiency of the dendritic-like BiVO4 photocatalysts for degradation of RhB solution was prominently improved from 34.4% to 91.4% under visible light irradiation only for 20 min. (C) 2016 Elsevier Ltd. All rights reserved.