Here, for the first time, it is reported that some Mn oxides after a few hours convert to a nanolayered Mn oxide when the compounds are used as water-oxidizing catalysts in a water electrolysis device at near neutral pH and in the presence of LiClO4. The new nanolayered Mn oxide is more active than other Mn oxides toward water oxidation. This result is very important for artificial photosynthetic systems that use Mn oxides as water-oxidizing catalysts.