The addition of lithium chloride promoted the coupling reaction of hydrocarbon solutions of poly(styryl)lithium (PSLi) and poly(isoprenyl)lithium (PILi) with 3-dimethylaminopropyl chloride to form the correspending omega-dimethylamino-functionalized polymers. Quantitative amine functionalization was achieved for PSLi and PILi in the presence of I and 10 equivalents, respectively, of Lid in benzene; the functionalization efficiency was only 67% for PSLi and 85% for PILi in the absence of LiCl. The polymer products were characterized by size exclusion chromatography, thin-layer chromatography, and amine end-group titration. The pure amine-functionalized polymers were isolated by silica gel column chromatography.