Abstract Although sufficient tolerance against attack by superoxide radicals (O 2 − ) has been mainly recognized as an important property for Li–O battery (LOB) electrolytes, recent evidence revealed that other critical factors also govern the cyclability, prompting a reconsideration of basic design guidelines LOB electrolytes. Here, we found LOBs equipped with N , N‐ dimethylacetamide (DMA)‐ba...