Mesoporous and microporous silica matrices were formed on indium tin oxide electrodes for liquid-phase voltammetry and as monoliths for solid-state voltammetry of aniline. The pore structure, which was verified by scanning probe microscopy and by surface area measurement, was directed by either control of pH during sol-gel processing or by inclusion of a templating agent. Whether aniline was included as a dopant in the sol-gel or as a component of the contacting liquid, the pore size influenced the coupling of the product of its electrochemical oxidation. With microporous silica, the dominant products were dimers and related short-chain products whereas with mesoporous silica, polymerization was suggested. As a step toward the formation of polyaniline (PANI) that is covalently anchored to the sol-gel, the electrochemistry of aniline was investigated using composites prepared from sols comprising tetraethyl orthosilicate (TEOS), 3-aminophenyl-[3-triethoxylsilyl)-propyl] urea (ormosil), and aniline in various ratios. Combinatorial chemistry identified that the optimum combination of silica precursors in terms of obtaining PANI was a 1:12 mole ratio of ormosil:TEOS. (C) 2004 Elsevier Ltd. All rights reserved.