Regulating internal electronic structure of photocatalysts via elements doping holds huge potential in tuning efficient charge transfer and boosting high-performance. Herein, molybdenum embedded bismuth tungstate (Bi2WO6) is employed to explore the electronic structures and various performances via the assistance of experimental verification and density function theory (DFT) simulation. The band structures and Mo ions doping behaviors of Bi2MoxW1-xO6 are systematically measured. Doping can induce the distortion of intrinsic electric density and internal electric-field, resulted in efficient charge transfer of Bi2Mo0.4W0.6O6. It exhibits much efficient photocatalytic activities under visible-light irradiation, also manifests huge potential as an anode material in lithium-ion batteries (LIBs) which is rarely reported before. This work may provide insights in the development of bismuth-based semiconductors in energy related applications. (C) 2018 Elsevier Inc. All rights reserved.