Rationally engineered p-n heterojunctions with the extensive heterogeneous interfaces is a promising method to pursue high charge carrier mobility and excellent photocatalytic activity in a wide range of applications. A porous mulberry-like BiVO 4 À Bi 2 O 3 composite with p-n heterojunctions was synthesized via a onepot hydrothermal approach. There exist intimate interfaces between the two semiconductors because of the in situ growth condition. The as-obtained BiVO 4 À Bi 2 O 3 heterojunctions exhibit excellent photocatalytic performance not only for CO 2 and Cr(VI) reduction, but also for NO removal under visible light irradiation in contrast to pure BiVO 4 . The CH 4 and CO yields for CO 2 reduction reaches 13.16 μmol g À 1 and 1.68 μmol g À 1 , about 47 and 25.7 times higher than that of pure BiVO 4 , and the highest apparent rate constant is about 56 times than that of BiVO 4 in the process of Cr(VI) reduction. Further detailed characterization reveals that the enhanced and stable photocatalytic reduction and oxidation activities can be attributed to the efficient transfer and spatial separation of the photoinduced carriers, resulting from not only p-n heterojunctions with matched band structures, but also intimate contact and the abundant interfaces between BiVO 4 and Bi 2 O 3 .