The photocatalytic reduction of CO2 has a great potential to produce fuels and chemicals, as well as, it reduces CO2 emission and addresses the environmental issues. To date single metal based catalysts still suffer from lower efficiency, uncontrollable selectivity and instability. In this study, hierarchical microspheres (HMs) of ZnV2O4 with VO2 impurity were synthesized through the single step reduction process, to explore highly efficient photocatalyst towards visible light responsive photocatalytic CO2 reduction. HMs of ZnV2O4 were successfully synthesized with mesoporous structure, higher surface area and functional under visible light irradiations. The highest yield of CO and CH3OH of 378 and 202 mu mole g-cat(-1) h(-1) were obtained over ZnV2O4 synthesized after 24 h of reaction time, respectively. The performance of optimized 3D HMs of ZnV2O4 for CO and CH3OH production was 2.30 folds and 10.7 folds higher than using ZnO/V2O5 composite sample, respectively. Other products detected with appreciable amounts were CH4 and C2H6. This reveals, HMs structure of ZnV(2)O(4 )not only allows the transfer of electrons towards CO2, but also provides short pathways for electron transfer and empty space in the microspheres will serve as the reservoirs to store the electrons, hence leading to enhanced photoactivity. In addition, VO2 presents in the sample further contribute to enhance performance of ZnV2O4 HMs due to enabling efficient charge carrier separation. The prolong stability of ZnV2O4 in the CO2 reduction system confirmed that 3D HMs structure provides controllable selectivity and stability. This brings to conclusions that fabrication of hierarchical structures will stimulate further development towards high performance photo-catalysts for the photocatalytic CO2 reduction to solar hydrocarbon fuels.