Two kinds of metal oxide-silver nanoparticles (Ag NPs) embedded in carbon nanofibers (CNFs) were prepared by electrospinning followed by calcination. The resulted nanofibers were characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, transmission electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. It indicated that MgO-Ag NPs and Al2O3-Ag NPs were well-distributed in the CNFs. This effective synthesis method can be used to prepare other composite nanofibers with functionality. MgO-Ag NPs-CNFs and Al2O3-Ag NPs-CNFs served as supported catalysts were used in the styrene epoxidation by TBHP. The Al2O3-Ag NPs-CNFs catalyst showed its high catalytic activity for the epoxidation of styrene (conversion: 46.45%, styrene oxide (SO) selectivity: 34.45%), as compared with the MgO-Ag NPs-CNFs catalyst. The addition of MgO or Al2O3 had the effect of a promoter in the catalyst system. These kinds of composite nanofiber membranes have proven effective catalytic activity and recyclability in the styrene epoxidation.