As the lightest metal, the reversible insertion/extraction properties of lithium have been key findings in lithium metal oxide chemistry. Lithium has been widely used in the oxygen evolution reaction (OER), and the reaction mechanism of lithium-mediated metal oxides has both similarities and uniqueness compared to typical dual metal oxides. Notably, the insertion/extraction of lithium during the OER is also crucial for the construction of novel surface reconstruction models. This review aims to provide the concepts of general OER pathways and key features of dual metal oxides for the OER. As a comparison then the development of lithium metal oxides for the OER is introduced and the chemistry underlying lithium metal oxide catalysts is unveiled. This review also examines the challenges remaining for the relevant catalysts, with prospects for further improving their OER activities.