The pyrolysis of metal-organic frameworks has emerged as a promising route to synthesize metal oxides with diverse phase compositions, morphologies, sizes and surface areas. The BiOBr/Bi24O31Br10/TiO2 (BBT) heterostructures have been achieved for the first time by calcining BiOBr/MIL-125(Ti) composite at 500°C in air. The BBT-2 composite exhibited the highest photocatalytic performance for degradation of RhB under visible light irradiation. The enhanced photocatalytic activity is attributed to narrower band-gaps and synergistic effect originating from the well-aligned straddling band-structures between BiOBr, Bi24O31Br10 and TiO2, also result in an faster interfacial charge transfer during the photocatalytic reaction. This work could be conductive to the design of heterostructured photocatalysts contained metal oxide by pyrolytic conversion of metal-organic frameworks for significantly improved photocatalytic performance. A novel BiOBr/Bi24O31Br10/TiO2 heterostructure was achieved by calcining BiOBr/MIL-125(Ti) composite and exhibited the photocatalytic performance for degradation of RhB. Display omitted •A novel BiOBr/Bi24O31Br10/TiO2 heterostructure was achieved by calcining BiOBr/MIL-125(Ti) composite.•The heterostructure exhibited the photocatalytic performance for degradation of RhB.•The enhanced photocatalytic activity is attributed to synergistic effect between BiOBr, Bi24O31Br10 and TiO2.•This work could be conductive to the design of heterostructured photocatalysts by pyrolytic conversion of MOF.