One-dimensional (1D) Bi2O3-Bi2O2.33 heterostructures were synthesized by calcining Bi2O2CO3-Bi(OHC2O4)center dot 2H(2)O precursors. Ultrathin Bi2O2.33 nanosheets were uniformly patched onto the porous Bi2O3 rod with well-matched lattice fringes, which increased the interface quality and then provided the smallest penetration barrier for electron-hole pairs transfer between Bi2O3-Bi2O2.33 interfaces. The photocatalytic performance of the obtained products was evaluated by the degradation of high-concentration methyl orange (MO) and phenol under solar/visible light irradiation. The results show that Bi2O3-Bi2O2.33 heterostructure displays higher photocatalytic activity than pure phase Bi2O3 and Bi2O2.33, and more encouragingly, 30 mg/L of MO (or phenol) can be completely degraded in 60 min under visible light irradiation using Bi2O3-Bi2O2.33 (S2) heterostructure as photocatalyst. This enhanced photocatalytic performance is ascribed to the synergistic effect of the suitable band alignment of the Bi2O3 and Bi2O2.33, high interface quality beween Bi(2)O(3)and Bi2O2.33 junctions and one-dimensional ordered nanostructure. This work would offer a novel route to design and fabrication of junction structures with high interface quality for photocatalytic applications. (C) 2016 Elsevier B.V. All rights reserved.