A convenient preparative approach to previously unknown, highly electrophilic C‐phosphorylated N‐arylsulfonylimines 1, based on fairly readily accessible α‐phosphorylated sulfonamides 5, has been developed. Compounds 1 react with trialkyl phosphites or ethyl diphenylphosphinite in the aza‐Perkow reaction scheme to give C,N‐diphosphorylated N‐dichlorovinylsulfonamides 8. On treatment with O‐ and S‐nucleophilic agents (alcohols, thiols, thiophenols), 1 forms addition products 12 and 15, the functionalized derivatives of α‐aminophosphonic acids, while interaction between 1 and mercaptoacetic acid proceeds with intramolecular cyclization of the intermediate adduct to produce the novel 2‐phosphorylated thiazolidinones 17. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)