Hierarchical nanostructures have lately garnered enormous attention because of their remarkable performances in energy storage and catalysis applications. In this study, novel hierarchical ZnV2O6 nanosheets, formulated by one-step solvothermal method, for enhanced photocatalytic CO2 reduction with H2O to solar fuels has been investigated. The structure and properties of the catalysts were characterized by XRD, FESEM, TEM, BET, UV-vis, Raman and PL spectroscopy. The hierarchical ZnV2O6 nanosheets show excellent performance towards photoreduction of CO2 with H2O to CH3OH, CH3COOH and HCOOH under visible light. The main product yield, CH3OH of 3253.84 mu mol g-cat(-1) was obtained over ZnV2O6, 3.4 times the amount of CH3OH produced over the ZnO/V2O5 composite (945.28 mu mol g-cat(-1)). In addition, CH3OH selectivity of 39.96% achieved over ZnO/V2O5, increased to 48.78% in ZnV2O6 nanosheets. This significant improvement in photo-activity over ZnV2O6 structure was due to hierarchical structure with enhanced charge separation by V2O5. The obtained ZnV2O6 hierarchical nanosheets exhibited excellent photocatalytic stability for selective CH3OH production. (c) 2017 Elsevier B.V. All rights reserved.