Electropolymerization of aniline was investigated in solutions of different pH from 1.0 to 12.1 without extra supporting electrolyte. FT-IR Spectra of the polymers display characteristic absorptions for polyaniline (PANI) including that for protonated PANI, although some of the polymers were obtained in solutions of high pH. PANI obtained from acidic solutions displayed the usual electroactivities in 0.5 mol center dot l(-1) H2SO4, while those obtained from solutions of pH 6.0 to 12.1 showed an unusual redox pair additionally on cyclic voltammograms at 0.04 V vs. SCE. This redox pair can be ascribed to the redox of phenazine ring, originated from the attack of nitrenium cation to PANI chain in the ortho-position. Electrocodeposition of PANI and SiO2 was conducted through electrophoresis of silica particles towards anode as aniline anodically electropolymerized. Energy dispersive X-ray diffraction (EDX) analysis and SEM inspection were performed on obtained PANI/SiO2 to investigate the composite film.