A novel chiral methacrylamide bearing perfluoropyrrolidino, groups was synthesized. Perfluoro(2-pyrrolidinopropionyl fluoride), the starting material, was prepared by electrochemical fluorination and resolved into enantiomeric derivatives by preparative high performance liquid chromatography (HPLC) performed with optically active 1-phenethylamine as the diastereomeric counterpart. The polymethacrylamide was obtained by radical polymerization. A clear, colorless, tough film of the polymer was formed by the solution-casting technique, which showed excellent water repulsion with a contact angle of water greater than 100 degrees. Column packings prepared by the coating of silica gels with the optically active polymer showed potential as the chiral stationary phase for HPLC resolving racemic 1,1'-bi-2-naphthol (separation factor = 1.56) with a hexane-isopropanol mixture as the eluent.