AbstractIn this study, both monofunctional and bifunctional nucleophiles, as well as the electrophile FNO, are reacted with perfluorovinyl amines. The perfluorovinyl amines CFCF2 and CFCF2 have been reacted with dimethylamine and diethylamine in the presence of small amounts of water to give CHFC(O)N(CH3)2 (1), CHFC(O)N(CH3)2 (2), and CHFC(O)N(C2H5)2 (3). With perfluorovinyl pyrrolidine and perfluorovinyl morpholine, ethanolamine gives the cyclized products CHF (4) and CHF (5), respectively. Reaction of the vinyl amines with (CH3)3SiOCH2CF3 in the presence of catalytic amounts of CsF results in the formation of cis‐ (6) and trans‐ (7) CFCF(OCH2CF3) and cis‐ (8) and trans‐ (9) CFCF(OCH2CF3). The electrophile FNO reacts slowly with perfluorovinyl pyrrolidine and perfluorovinyl morpholine, and more rapidly with (CF3)3CCFCF2 to give CF(NO)CF3 (10), CF(NO)CF3 (11) and (CF3)3CF(NO)CF3 (12), respectively. Single crystal X‐ray analysis is used to confirm the identity of the product obtained from the controlled hydrolysis of the sultone of perfluorovinyl pyrrolidine as the sulfonic acid anhydride C(O)CF2OS(O)2OCF2C(O) (13). The X‐ray crystal structure of perfluorosuccinic acid monohydrate (14), which is obtained when the perfluorovinyl pyrrolidine sultone is hydrolyzed in excess water, is also reported for the first time.