The cationic palladium(II) complex [(R,R-Me-DuPHOS)Pd(Me)(CH3CN)]+BF4- (R,R-Me-DuPHOS = 1,2-bis[(2R,5R)-2,5-dimethylphospholano]benzene) was found to catalyze the perfectly alternating copolymerization of fluorinated allylbenzene derivatives with carbon monoxide, leading to functional polymers containing pendant fluorinated groups. The copolymers each exhibited relatively high hydrophobicity, as determined by goniometry. The alt-allylpentafluorobenzene-carbon monoxide copolymer was found to significantly increase the water contact angle of poly(methyl methacrylate) when blended in small amounts with the latter.