Enzymatic polymerization of bis(2,2,2-trifluoroethyl) sebacate and aliphatic diols was investigated with the purpose of obtaining a polyester of as high as possible average molecular weight. The reaction was carried out at 37°C, and vacuum was applied to shift the equilibrium forward by removal of the 2,2,2-trifluoroethanol formed. The results showed that the elimination of alcohol formed was critical for a high degree of polymerization. Among the four lipases studied, Mucor miehei lipase was the best biocatalyst for polytransesterification and diphenyl ether was the best solvent for the polymerization of bis(2,2,2-trifluoroethyl) sebacate with 1,4-butanediol. The highest average molecular weight (Mw) of 46,400 g mol-1 (degree of polymerization = 184) was obtained when 0.51 m (187 g l-1) bis(2,2,2-trifluoroethyl) sebacate was polymerized with 0.51 m (46 g l-1) 1,4-butanediol in diphenyl ether for 168 h (7 days) with 36.5% M. miehei lipase powder.