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A novel Bi 2 MoO 6 /Bi 4 V 2 O 11 heterostructured photocatalyst was successfully fabricated using a facile one-pot solvothermal method. This heterojunction consists of homogeneous dispersed Bi 4 V 2 O 11 nanocrystals anchored on the surface of Bi 2 MoO 6 nanoflakes, endowing the heterojunction with nanosized interfacial contact. Based on the favorable interfacial contact, the band alignment at the heterojunction effectively facilitated photo-generated carrier transfer, which was verified by photoelectrochemical and photoluminescence measurements. Thereby, in contrast with pristine Bi 2 MoO 6 and Bi 4 V 2 O 11 , the as-synthesized heterojunction with nanoscale contact exhibited significantly enhanced photocatalytic activity towards the degradation of MB and the reduction of Cr(vi). In addition, the as-fabricated Bi 2 MoO 6 /Bi 4 V 2 O 11 heterojunction exhibited good cycling stability for MB degradation after 4 cycles. Finally, a plausible photocatalytic mechanism for MB degradation over the Bi 2 MoO 6 /Bi 4 V 2 O 11 heterojunction was discussed in detail. This work not only reports a highly efficient photocatalyst but also sheds light on the design and optimization of a heterojunction., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)