The most ideal substitute for Pt/C to catalyze the oxygen reduction reaction (ORR) is the transition metal and nitrogen co-doped carbon-based material (TM-N-C). However, large particles with low catalytic activity are formed easily for the transition metals during high-temperature carbonization. Herein, PAN nanofibers uniformly distributed with FeCl3 were coated with SiO2 and then carbonized to obtain Fe–N–Si tri-doped carbon nanofibers catalyst (Fe–N–Si-CNFs). The SiO2 can further anchor the Fe atoms, thus preventing agglomeration during the carbonization process. Meanwhile, Si atoms have been doped in CNFs during this process, which is conducive to the further improvement of catalytic performance. The Fe–N–Si-CNFs catalyst has a 3D network structure and a large specific surface area (809.3 m2 g−1), which contributes to catalyzing the ORR. In alkaline media, Fe–N–Si-CNFs exhibits superior catalytic performance (E1/2 = 0.86 V vs. RHE) and higher stability (9.6% activity attenuation after 20000s) than Pt/C catalyst (20 wt%).