Defect engineering has emerged as an efficient and promising strategy in the field of semiconductor materials, while assembling controllable vacancy defects and two-dimensional (2D) heterostructures into together is a great challenge. In this work, 2D heterostructures of WS2/WO3 center dot H2O doped with oxide vacancies have been synthesized successfully with assistance of supercritical CO2. And the fascinating heterostructures have been evidenced by their significant photocatalysis performance for water splitting. Theoretical calculations demonstrate that the vacancies in the obtained 2D heterostructures can narrow the effective band gap and improve the carrier separation efficiency as well. This wok will provide a positive strategy for fabrication of advanced photocatalyst and a new perspective in understanding the synergistic effect of structural and electronic regulations. (C) 2017 Published by Elsevier B.V.