One-dimensional Bi₂O₃–Bi₄V₂O₁₁ heterostructures with enhanced visible light photocatalytic performance were synthesized by high temperature calcination of Bi(OHC₂O₄)·2H₂O–Bi₂VO_5.5 precursors. The Bi₄V₂O₁₁ nanosheets uniformly grew on the Bi₂O₃ porous rods by crystallographic-oriented epitaxial growth, which increased the interface quality and then provided the smallest penetration barrier for electron–hole pair transfer between Bi₂O₃–Bi₄V₂O₁₁ interfaces. The photocatalytic performance of the obtained products was evaluated by degradation of phenol and methyl orange (MO) with high concentration under visible light irradiation. The results show that the Bi₂O₃–Bi₄V₂O₁₁ heterostructure displays higher photocatalytic activity than pure phase Bi₂O₃ and Bi₄V₂O₁₁, and more encouragingly, 40 mg L⁻¹ of phenol can be completely degraded in 30 min under visible light irradiation using the Bi₂O₃–Bi₄V₂O₁₁ (DS-2) heterostructure as the photocatalyst. This enhanced photocatalytic performance is ascribed to the synergistic effect of the suitable band alignment of the Bi₂O₃ and Bi₄V₂O₁₁, high interface quality and one-dimensionally ordered nanostructure. Radical scavenger experiments indicate that holes (h⁺) and superoxide radicals (˙O₂⁻) were the main active species for phenol (and MO) degradation during the photocatalytic process. This work would offer a simple route to design and fabricate junction structures with high interface quality for photocatalytic applications.