1,2-Dichlorotetrafluorocyclobutene-1 (1), 1,2-dichlorohexafluorocyclopentene-1 (2), and 1,2-dichlorooctafluorocyclohexene-1 (3) react with tetraaza macrocyclic amines (1,4,7,10-tetraazacyclododecane (A), 1,4,7,10-tetraazacyclotridecane (B), 1,4,8,11-tetraazacyclotetradecane (C), 1,4,7,11-tetraazacyclotetradecane (D), 1,4,8,12-tetraazacyclopentadecane (E), and 1,5,9,13-tetraazacyclohexadecane (F)) by heating at 70-80-degrees-C for 8-12 h in the presence of stoichiometric amounts of triethylamine in benzene under nitrogen. Cycloalkene 1 forms products in the ratio of 1:3, cycloalkene 2 gives 1:2 products, and cycloalkene 3 results in 1:1 substituted derivatives of the tetraazamacrocyclic amines A-F, respectively, in good yields. With all three dichloroperfluorocyclic alkenes (1-3), macrocyclic amine A forms solid compounds that exhibit sharp melting points whereas other substituted derivatives of the tetraazamacrocyclic amines B-F are viscous oils. All of these substituted derivatives are very stable and do not decompose on exposure to moist air at ambient temperature over long periods. The crystal structures of 1,4,7-tris(chlorotetrafluorocyclobutenyl)-1,4,7,10-tetraazacyclododecane (1A) and 1,7-bis(chlorohexafluoropentenyl)-1,4,7,10-tetraazacyclododecane (2A) have been determined by X-ray diffraction methods.