Abstractω‐Dimethylaminopolystyrenes can be synthesized in quantitative yields by reacting poly(styryl)lithium with 1‐(4‐dimethylaminophenyl)‐1 ‐phenylethylene (1). The resulting polymeric dimethylamino‐substituted 1,1‐diphenylalkyllithium was terminated with methanol or reacted with butadiene to form a diblock copolymer, poly(styrene‐b‐butadiene), with the dimethylamino group at the interface between the blocks. α‐Dimethylaminopolystyrene and α‐dimethylaminopoly‐(methyl methacrylate) were synthesized by using the adduct of1withsec‐butyllithium as initiator, α,ω‐Bis(dimethylamino)polystyrene was prepared by using the functionalized initiator and then terminating the resulting dimethylaminopoly‐(styryl)lithium with1. The amine‐functionalized polymers were characterized by end‐group titration, size exclusion chromatography, thin‐layer chromatography, vapor phase osmometry, elemental analysis and both1H and13C NMR spectroscopy. All experimental evidence is consistent with quantitative functionalization