In order to synthesize N,N-di-(polyoxyethylene) perfluoroacyl amines and the surface active monoperfluoroacyl aza crown ethers, it is performed as follow. Six of N,N-di(polyoxyethylene) perfluoro acyl amines were synthesized from perfluoroalkanoic acids with ethanol followed by oxyethylation with triethylene glycol mono chloride or tetra ethylene glycol mono chloride and six of N-perfluor acyl monoaza crown ethers by cyclization of corresponding N,N-di(polyoxy ethylene} perfluoro acyl amines with p-toluene suflonic chloride-NaOH/dioxane, p-toluene sulfonyl chloride KOH/dioxane and benzene sulfonic chloride-KOH/dioxane systems.