In this paper, a facile two-step synthesis route combining an electrospinning technique and vapor transport deposition method has been accepted as a straightforward protocol for the exploitation of ZnO/carbon nanofibers (CNFs) hierarchical heterostructures which are composed of ZnO nanorods on the surface of CNFs. Photocatalytic tests display that the ZnO/CNFs heterostructures possess degrading Rhodamine B (RB) at a much higher rate than pure ZnO. The enhanced photocatalytic activity could be attributed to the effective separation of photo-generated carriers driven by the photoinduced potential difference, which is generated at the ZnO/CNFs heterojunction interface. Moreover, the heterostructures could be reclaimed easily by sedimentation without a decrease of the photocatalytic activity. Such simple and versatile strategy can provide a general way to fabricate other heterostructures, such as TiO2/CNFs.