New mechanisms of oxygen reduction on perovskite related oxides LaLi0.1M0.1Fe0.8O3-d (M = Fe, Co, Ni) and a rock salt type oxide Li0.1Ni0.9O have been proposed. Based on these mechanisms, a comparison of catalytic activity of the oxides in the temperature range 820–1000 K has been done. It has been shown that catalytic activity of LaLi0.Co0.1Fe0.8O3-d oxide exceeds the activity of Li0.1Ni0.9O below 970 K