The aggregation and the rapid restructuring of the photoinduced electron−hole pairs restructuring in the process of photoelectric response remains a great challenge. In this study, a kind of Multi-walled carbon nanotubes loaded Alpha-Fe₂O₃ (CNTs/α-Fe₂O₃) heterostructure composite is successfully prepared via the one-step method. Due to the synergistic effect in the as-prepared CNTs/α-Fe₂O₃, the defect sites and oxygen-containing functional groups of CNTs can dramatically improve the interface charge separation efficiency and prevent the aggregation of α-Fe₂O₃. The improved photocurrent and enhanced hole–electron separation rate in the CNTs/α-Fe₂O₃ is obtained, and the narrower band gap is measured to be 2.8 ev with intensive visible-light absorption performance. Thus, the CNTs/α-Fe₂O₃ composite serves as an excellent visible light photocatalyst and exhibits an outstanding photocatalytic activity for the cationic dye degradation of rhodamine B (RhB). This research supplies a fresh application area forα-Fe₂O₃ photocatalyst and initiates a new approach for design of high efficiency photocatalytic materials.