Heterophase junction construction is a powerful means of inhibiting recombination of photoinduced charge carriers. Herein, we prepared BiVO4/Bi4V2O10 porous heterophase nanospheres assembled by nanoflakes through a facile solvothermal process. The crystal structure of the porous nanospheres can be easily regulated from mixed phase of BiVO4 and Bi4V2O10 to pure BiVO4 by changing the solvothermal reaction time. The formation of heterophase junction BiVO4/Bi4V2O10 can greatly enhance the transfer and separation rate of photogenerated charge carriers. Meanwhile, the porous nanoflake-based nanosphere structure can enhance visible light utilization and organic pollutants adsorption. Benefiting from the synergy effects of these positive factors, the optimal BiVO4/Bi4V2O10 exhibits excellent visible light photocatalytic performance and cycling capability for the degradation of organic pollutants.