Hollow perovskite oxide La0·5Sr0·5MnO3 nanospheres are synthesized by using carbon spheres as template in the presence of citric acid. Among the samples investigated in this work, the one obtained at a sintering temperature of 700 °C exhibits the highest catalytic activity in the oxygen reduction reaction (ORR) in an alkaline electrolyte. The electrochemical measurement data shows that the sample has a positive onset potential (0.860 V) and a high limiting current density (6.48 mA cm−2). Furthermore, the catalyst shows a high selectivity towards methanol and a better stability than a commercial Pt/C catalyst. The hollow La0·5Sr0·5MnO3 nanoshperes described in this manuscript hold a great promise for applications in metal-air batteries and alkaline fuel cells.