We report the facile synthesis of 3-trifluoromethyl-6-methyl-1,4-dioxane-2,5-dione and ring-opening polymer-ization of the fluoro-lactide monomer to prepare polylactides composed of trifluoromethyl and methyl pendent groups on each repeat unit (FPLA). Molecular weights of the prepared polymers correlated well with the initial molar ratio of monomer to initiator and were found to range from 6.6 to 22.5 kDa as determined by H-1 NMR spectroscopy. GPC analysis revealed an M-n of up to 16.5 kDa. H-1, C-13, and F-19 NMR spectroscopy were consistent with the structures of the lactide monomer isomers, and H-1 NMR analysis was consistent with polymer backbones of alternating trifluoromethyl- and methyl-substituted lactate constituents. Glass transition temperature (T-g) and decomposition temperature (T-d) of the new FPLA were found to be 39 and 225 degrees C by DSC and TGA, respectively. Additionally, we prepared amphiphilic block copolymers of FPLA and poly(ethylene glycol) (PEG). Specifically, FPLA-b-PEG diblocks and FPLA-PEG-FPLA triblocks were synthesized by using PEG monomethyl ether (mPEG) or PEG as alcohol initiators, respectively. We observed the formation of vesicles or wormlike micelles from the particles of FPLA-PEG-FPLA in dilute aqueous solution by transmission electron microscopy (TEM), suggesting potential applications for drug delivery.