Abstract Aurivillius oxide semiconductors are important photocatalyst because of their unique electronic structure and layered crystal. In this paper, two kinds of Aurivillius oxide semiconductors heterostructures based on Bi4Ti3O12 nanofibers frameworks and BiOCl nanosheets are successfully synthesized by combining the electrospinning technique and solvothermal method. The high-resolution transmission electron microscopy results reveal that an intimate interface between Bi4Ti3O12 nanofibers and BiOCl nanosheets forms in the heterojunctions. Photocatalytic tests show that the BiOCl/Bi4Ti3O12 heterostructures exhibit enhanced photocatalytic activity than bare Bi4Ti3O12 and BiOCl, mainly owing to the photoinduced interfacial charge transfer based on the photosynergistic effect of the BiOCl/Bi4Ti3O12 heterojunction. At the end, the photocatalytic mechanism with O2− production was studied.