We report the synthesis of new gradient fluorinated copolymers with complexing groups and soluble in supercritical carbon dioxide (scCO(2)). Poly(1,1,2,2-tetrahydroperfluorodecyl acrylate-co-acetoacetoxyethyl methacrylate) (poly(FDA-co-AAEM)) and poly(1,1,2,2-tetrahydroperfluorodecyl acrylate-co-vinylbenzylphosphonic acid diethylester) (poly(FDA-co-VBPDE)) gradient copolymers were synthesized by reversible addition fragmentation chain transfer polymerization in a,a,a-trifluorotoluene. Poly(1,1,2,2-tetrahydroperfluorodecyl acrylate-co-vinylbenzylphosphonic diacid) (poly(FDA-co-VBPDA)) gradient copolymer was efficiently obtained by cleavage of the phosphonic ester groups of poly(FDA-co-VBPDE). The cloud points of these gradient copolymers in dense CO2 were measured in a variable volume view cell at temperatures between 25 and 65 C. The gradient copolymers show very good solubility in compressed CO2 with the decreasing order: poly(FDA-co-AAEM).:; poly(FDA-co-VBPDE) > poly(FDA-co-VBPDA). Following a green chemistry strategy, poly(FDA-co-AAEM) gradient copolymer was successfully synthesized in scCO(2) with a good control over number-average molecular weight and composition. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5448-5460, 2009