It is desirable to develop an efficient visible-light-driven photocatalyst for practical application to degrade highly-noxious pollutants. Herein, the hydrogenation hierarchical flower-like Bi2MoO(6) hollow spheres (H-BMO-X, where X represents the different hydrogen calcination temperatures) have been successfully fabricated by a solvothermal-surface hydrogenation process. The as-prepared nano-photocatalyst H-BMO-300 clearly exhibits a photocatalytic reaction apparent rate constant k for high-noxious pollutants by similar to 3-times higher than pristine Bi2MoO(6). Moreover, the resultant H-BMO-300 sample with a narrow bandgap of similar to 2.70 eV possesses surface oxygen vacancy defects. Based on the scanning Kelvin probe and surface photovoltage spectroscopy, it is deduced that the photo catalytic activities are attributed to the surface oxygen vacancy of H-BMO-X favoring the electron-hole pair's separation. The enhanced photocatalytic performance can be ascribed to the synergistic effect of surface defects favoring efficient electron-hole separation and the hollow hierarchical structure benefiting the utilization of visible light, which provides more surface-active sites. This work provides a viable route to perceptibly enhance the photocatalytic activities of H-BMO-300 for environmental remediation with good mineralization properties. (C) 2018 Elsevier Inc. All rights reserved.