Bi2FeVMoO10 [(Bi0.8Fe0.4)(MO0.4V0.4)O-4] was prepared via facile co-precipitation route. It has a tetragonal Scheelite structure derived by cation substitutions in monoclinic BiVO4. Rietveld refinements of Bi2FeVMoO10 were performed in body-centered tetragonal Scheelite. The morphological property was tested via SEM, EDX, and TEM measurements. The optical property was measured by UV-vis absorption spectrum. Bi2FeVMoO10 shows a narrower band gap of 2.07 eV than the monoclinic BiVO4 and alpha-Bi2Mo3O12. The photo-degradation experiments of Rhodamine-B (RhB) dye solutions were conducted. Bi2FeVMoO10 nanoparticles have more efficient photocatalytic ability on RhB degradation than that of BiVO4 and alpha-Bi2Mo3O12. The results were discussed on the Scheelite structure characteristics such as complicated optical absorption centers, loose space in the lattice because of the vacancies, large dispersion in the CB and VB electronic components and the Fe3+/Fe2+ redox couples. This multicomponent Scheelite oxide could have potential applications in environment protection.