Polymers bearing a single alkyl chloride at the chain end were synthesized using anionic polymerization techniques. Specifically, living polystyrene (PS) anions were treated with commercially available (4-chlorobutyl)dimethylchlorosilane and found to react chemoselectively at the electrophilic silicon atom.(1) The pendant alkyl chloride on these PS chains was subsequently transformed into alkyl azide and aliphatic amine functionalities. The gel permeation chromatograms for the synthesized polymers were found to have relatively narrow molecular weight distributions (M-w/M-n < 1.09) after the end-capping reaction. Nuclear magnetic resonance (NMR) spectroscopy and gel permeation chromatography (GPC) studies were used to quantify the degree of functionalization.