Here, we report the results of the comparative studies of the photostimulated hydrophilic behavior of heterostructured TiO2/BiVO4 and ZnO/BiVO4, and mono-component TiO2 and ZnO nanocoating surfaces. The chemical composition and morphology of the synthesized nanocoatings were characterized by XPS, SEM, and AFM methods. Electronic energy structure of the heterostructure components (band gap, top of the valence band, bottom of the conduction band, and Fermi level position) were determined on the basis of experimental results obtained by XPS, diffuse reflectance spectroscopy and Kelvin probe methods. According the electronic energy structure, ZnO/BiVO4 and TiO2/BiVO4 heterostructures correspond to the type I and type II heterostructures, respectively. The difference in the type of heterostructures causes the difference in the charge transfer behavior at heterojunctions: type II TiO2/BiVO4 heterostructure favors to and the type I ZnO/BiVO4 heterostructure prevents the photogenerated hole transfer from BiVO4 to the outer layer of the corresponding metal oxide. The results of the comparative studies show that interaction of the photogenerated holes with surface hydroxy-hydrated multilayers is responsible for the superhydrophilic surface conversion accompanying the increase of the surface free energy and work function. Formation of the type II heterostructure leads to the spectral sensitization of the photostimulated surface superhydrophilic conversion.