Poly(styrene sulfonate) (PSS) tethered polyhedral oligomeric silsesquioxane (POSS-PSS) was synthesized and used as star-like dopant for the preparation of core-shell polyaniline/POSS-PSS (PANI/POSS-PSS) nanoparticles. The prepared aqueous emulsion shows good processibility and high stability. The electrochemical characteristics and electrochromic properties of PANI/POSS-PSS were studied. In comparison with polyaniline (PANI) doped with linear PSS dopant, the star-like POSS-PSS dopant renders PANI/POSS-PSS-based electrochromic device higher optical contrast and faster switching speed owing to the faster ion transportation resulting from the porous morphology of PANI/POSS-PSS. (C) 2011 Elsevier B.V. All rights reserved.