Electronictuning: Nitroxylradical 1 is shown to be an efficient catalyst for the oxidation of secondary alcohols, and promotes oxidation through an oxoammonium species which is highly reactive because of the adjacent electron‐withdrawing ester groups. Chemoselectiveoxidation of benzylic alcohols in the presence of aliphatic alcohols is observed and is proposed to proceed by a rate‐determining hydride