The construction of bismuth-rich heterostructures is an important strategy to improve the performance of bismuth-based visible photocatalytic materials. In this study, the binary heterojunction BiOBr/Bi24O31Br10 (BOB) with efficient visible photocatalytic activity was constructed by in situ induced growth of BixOyBrz on the surface of BiOBr, and the multivariate heterojunction composite BiOBr/Bi24O31Br10/Ti3C2 (BOBT) was synthesized by using Ti3C2 as an electron acceptor. It was shown that the solvothermal pH, Bi/Br and calcination temperature had a strong influence on the composition and crystalline structure of BOBT. The optimized synthesis conditions were pH=8, Bi/Br=1/1 (molar ratio), and calcination temperature of 400℃. The introduction of Mxene significantly enhanced the visible-light responsiveness and photoelectric efficiency of BOBT. The visible light-catalyzed degradation of complex conjugated systems containing aromatic and azo structures by BOBT was synchronously accompanied by benzene ring opening, demonstrating an efficient visible light degradation capability. BOBT has a reduced reduction current peak compared to BOB, can rapidly reduce Cr (VI), and improves the photocatalytic hydrogen production efficiency by nearly three times compared to BiOBr without the addition of Pt additives. This study provides fundamental data for the construction of efficient bismuth-based visible photocatalytic materials and their applications.