A deconstructive oxygenation of unstrained primary cycloalkanamines has been developed for the first time using an auto‐oxidative aromatization promoted C(sp3)−C(sp3) bond cleavage strategy. This metal‐free method involves the substitution reaction of cycloalkanamines with hydrazonyl chlorides and subsequent auto‐oxidative annulation to in situ generate pre‐aromatics, followed by N‐radical‐promoted ring‐opening and further oxygenation by 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO) and m‐cholorperoxybenzoic acid (mCPBA). Consequently, a series of 1,2,4‐triazole‐containing acyclic carbonyl compounds were efficiently produced. This protocol features a one‐pot operation, mild reaction conditions, high regioselectivity and ring‐opening efficiency, broad substrate scope, and is compatible with alkaloids, osamines, and peptides, as well as steroids.