NiMgMn Layered Double Hydroxide (LDO) has been rationally designed for the efficient oxidative cleavage of 1,2-diols, utilizing molecular oxygen exclusively as the oxidizing agent without the need for additives. This engineered NiMgMn-LDO contains catalytically active Mn³⁺ species, which are stabilized by Ni²⁺. Additionally, it is endowed with numerous basic sites contributed by Mg species. These features bestow upon NiMgMn-LDO a dual functionality that significantly enhances its catalytic efficacy. Consequently, this catalyst demonstrates excellent catalytic prowess and robust tolerance in the aerobic oxidative cleavage of benzyl 1,2-diols.