Functionalized star polymers with tetraaniline on their surface have been successfully prepared by substitution reaction of N-succinimidylterminated star polymers with tetraaniline. A novel functional initiator bearing N-succinimidyl group was used in atom transfer radical polymerization (ATRP) of styrene, and polystyrenes (PSts) having N-succinimidyl groups with narrow molecular weight distribution were obtained. The star polymers with reactive N-succinimidyl groups on their surface were synthesized by ATRP of divinylbenzene (DVB). The N-succinimidylterminated PSt, polymer stars with surface N-succinimidyl groups and the PSt-b-tetraaniline stars were characterized by H-1 NMR spectroscopy, FT-IR and gel permeation chromatography. (c) 2006 Elsevier Ltd. All rights reserved.