To overcome the shortcomings of high cost and rare sources of precious metal based catalysts, the catalytic characteristics of reduced graphene oxide (rGO) supported (N, F)-co-doped TiO2 hybrid (TiO2/rGO) for oxygen reduction are investigated. Results show that the onset potential of oxygen reduction reaction (ORR) under the catalysis of TiO2/rGO is about −0.20 V (vs. Hg/Hg2Cl2). The corresponding electron transfer number of ORR is 3.98, which means that the ORR is major happened through a 4-electron process. TiO2/rGO catalyst has high catalytic for ORR and better stability than the commercial Pt/C catalytic performance in alkaline electrolyte. TiO2/rGO catalyst shows great promise as a high activity non-precious metal catalyst for ORR.