The efficient synthesis of omega-epoxide-functionalized macromonomers has been achieved by optimizing the reaction of polymeric organolithium compounds (PLi) with epichlorohydrin (EPC). The addition of epichlorohydrin to a benzene solution of poly(styryl)lithium (M(n) = 2 x 10(3) g/mol) forms the omega-epoxide-functionalized polystyrene in only 9% yield; the major products correspond to dimeric species (70%). Inverse addition of epichlorohydrin reduces the yield of dimer to 22% (16% ring-opened dimer and 6% nonfunctional) and increases the epoxidation yield to 28%; the other products correspond to unfunctionalized polymer (18%) and the ring-opened product (32%). Addition of tetrahydrofuran (THF) to the solutions of PLi and EPC decreases the dimer yield to 10% and increases the epoxide functionalization to 74% for poly(styryl)lithium and to 80% for poly(styrene-b-butadienyl)lithium. By reaction of the polymeric chain ends with 1,1-diphenylethylene (DPE) to form the corresponding polymeric (1,1-diphenylalkyl)lithium, functionalization yields increase to 83% with 4% dimer in benzene. After DPE end-capping and in the presence of THF, the epoxide functionalization yields increase to 91-97% with < 1% dimer. The omega-epoxide-functionalized polymers have been purified by column chromatography, and the epoxide functional groups have been characterized by H-1 and C-13 NMR and FTIR spectroscopy. Quantitative determination of the amount of epoxide functional groups in polymers was effected by perchloric acid/tetraethylammonium bromide titration.