A series of sulfonamido-substituted oxime-ethers have been synthesized by the reaction of donor-acceptor aziridines with aldo- and keto-oximes through C-C bond cleavage. Nucleophilic attack by an oxime hydroxyl group on the in situ-generated azomethine ylide rather than the routine cycloaddition reaction draws the novelty of the developed methodology. Selective protection of the oxime hydroxyl group is observed in the presence of phenolic -OH, which made the protocol enriched. In terms of a synthetic point of view, the uniqueness had been drawn further as it occurred at room temperature and within 30 min. Participation of a wide range of aziridines with a series of aldo- and keto-oximes made the developed methodology generalized by creating a novel library of substituted oxime-ethers.