Manganese oxide is one of the most extensively studied electrocatalysts for oxygen reduction reaction (ORR) due to its high abundance and environmental friendliness. In this work, cerium ion intercalated birnessite-type manganese oxide (δ-MnO2) dispersed on carbon (CeMnO2/C) with high-efficient oxygen reduction reaction(ORR) electrocatalytic ability in alkaline media is prepared via facile aqueous reactions for the first time. The as-prepared catalyst shows morphology like quasi special nanospheres intertwined by plenty of nanorods just like knitting wool balls. Compared with MnO2/C, the onset and half-wave potential of 4.8% CeMnO2/C shift positively 27 and 57 mV, respectively, and are close to those of Pt/C. The oxygen reduction reaction occurring on 4.8% CeMnO2/C undergoes a 4-electron transfer pathway with the HO2 − yield lee than 2%, which is much lower than that produced on Pt/C. The CeMnO2/C catalyst also exhibits excellent long-term stability with current retention of 96.4% after aging for 40000 s. The aluminum-air battery applying 4.8% CeMnO2/C as cathode catalyst gives out the peak power density of 348.8 mW cm−2 in 4 M KOH aqueous solution. After more than 300-h discharging, the voltage degradation of 4.8% CeMnO2/C is only 2% per 100 h. In all, the excellent performance of the Ce-intercalated MnO2/C demonstrates its enormous potential as ORR catalyst in metal-air batteries.