Tiny Fe3O4 nanoparticles (Fe3O4NP) were successfully immobilized on the surface of porous silica nanofibers (PSNF) to form a novel hybrid Fenton-like catalyst of Fe3O4/PSNF through an in situ high-temperature decomposition method. The crystalline phase, microstructure and specific properties of Fe3O4/PSNF were characterized in detail. It was found that the Fe3O4NP with cubic spinel structure and diameter of 10-80 nm was grown on the surface of PSNF through interfacial Fe-O-Si bond. The surface of PSNF was partly covered by Fe3O4NP, which made the surface hydroxyl groups of silanol well maintained in Fe3O4/PSNF. The Fenton-like catalytic performances of Fe3O4/PSNF and naked Fe3O4NP were evaluated through a series of kinetic tests on degradation of Rhodamine B. The results show that the Fe3O4/PSNF has much higher adsorption capacity and Fenton-like catalytic activity than those of naked Fe3O4NP. Besides, the Fe3O4/PSNF also shows good stability and recyclability, and as a result, the novel catalyst is easily separated by magnetic method and reused for further reaction. It is proposed that the PSNF significantly improves the catalytic activity by making a highly dispersed Fe3O4NP and providing abundant micro/mesopores and a large surface area with strong adsorptive and hydrophilic properties.