A new monomer, octa(thiophenephenyl)silsesquioxane (OThiophenePS) was synthesized via click chemistry. The chemical structure of OThiophenePS was characterized by nuclear magnetic resonance (H-1 NMR) and Fourier transform infrared (FT-IR) spectroscopies. Electrochemical polymerization of pyrrole with OThiophenePS was performed resulting in polypyrrole-attached, polyhedral oligomeric silsesquioxane (OPS-PPy). The spectroelectrochemical studies show that the electrochromic properties of (OPS-PPy) are superior to those of polypyrrole (PPy). This great improvement can be attributed to the more accessible doping sites and the facile ion movement during the redox switching brought by the loose packing of the PPy chains. (C) 2008 Elsevier Ltd. All rights reserved.