Fabrication of 3D hierarchical structure of BiOCl/TiO2 heterojunction with high energy (001) facet exposed, which avoids aggregation problem for practical usage. Complete photocatalytic mineralization of gaseous benzene into CO2 and H2O without any decay after 5 cycles. Proved interfacial charge transfer behavior between BiOCl and TiO2 by both experimental and theory calculation data. Benzene scavenging effect by surface oxygen vacancies on (001) facet of BiOCl.