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Reducing charge-discharge overpotential of transition metal oxide catalysts can eventually enhance the cell efficiency and cycle life of Li-O2 batteries. Here, we propose that crystal phase engineering of transition metal oxides could be an effective way to achieve the above purpose. We establish controllable crystal phase modulation of the binary MnxCo1-xO by adopting a cation regulation strategy. Systematic studies reveal an unprecedented relevancy between charge overpotential and crystal phase of MnxCo1-xO catalysts, whereas a dramati