In recent years, Janus materials have become a research hotspot in the field of materials science; however, fabricating inorganic Janus-like nanofibers (NFs) is still a challenge. Herein, we report novel ZnO/NiO Janus-like NFs with efficient photocatalytic performance via an electrospinning method followed by calcination treatment. The morphology, structure, chemical composition and crystallinity of ZnO/NiO Janus-like NFs were studied in detail via SEM, TEM, HRTEM, EDS, FT-IR, XPS and XRD, indicating that the NFs had a perfect Janus-like structure composed of ZnO and NiO. A series of photocatalytic experiments were carried out in aqueous organic dye solutions under 365 nm UV radiation for 1 h, with the degradation rate of malachite green able to reach 96%, proving that the NFs have great potential in the field of organic dye degradation. Furthermore, a reasonable catalytic mechanism for the ZnO/NiO Janus-like NFs was proposed, which was discussed from the view of electron-hole pairs and p-n junctions. In short, the method in our work is expected to become a new way of effectively preparing functional inorganic Janus-like NFs.