Oxygen electrocatalysis, as the pivotal circle of many green energy technologies, sets off a worldwide research boom in full swing, while its large kinetic obstacles require remarkable catalysts to break through. Here, based on summarizing reaction mechanisms and in situ characterizations, the structure–activity relationships of oxygen electrocatalysts are emphatically overviewed, including the influence of geometric morphology and chemical structures on the electrocatalytic performances. Subsequently, experimental/theoretical research is combined with device applications to comprehensively summarize the cutting‐edge oxygen electrocatalysts according to various material categories. Finally, future challenges are forecasted from the perspective of catalyst development and device applications, favoring researchers to promote the industrialization of oxygen electrocatalysis at an early date.