Nanocomposites were successfully synthesized by the oxidative polymerization of p‐anisidine and/or aniline monomers (at initial “p‐anisidine:aniline” mole ratios of “100 : 0,” 50 : 50,” and “0 : 100”) with titanium(IV) oxide nanoparticles, in the presence of hydrochloric acid as a dopant with ammonium persulfate as an oxidant. The morphological, structural, conductivity, and electrochemical properties of the synthesized nanocomposites were studied using Transmission Electron Microscopy, X‐ray diffraction, Fourier transform infrared spectroscopy, and UV–vis spectroscopies. The presence of polymer on TiO2 nanoparticles in samples nanocomposites was confirmed by the Transmission Electron Microscopy coupled with Energy Dispersive X‐ray Spectroscopy. The thermal stability of samples nanocomposites were evaluated using the Thermogravimetric Analysis. Electrical conductivity of nanocomposites obtained is in the range of 0.08 − 0.91 S cm−1. The electrochemical behavior of the polymers extracted from the nanocomposites has been analyzed by cyclic voltammetry. Good electrochemical response has been observed for polymer films; the observed redox processes indicate that the polymerization on TiO2 nanoparticles produces electroactive polymers. These composite microspheres can potentially be used in commercial applications as fillers for antistatic and anticorrosion coatings. POLYM. COMPOS., 38:E254–E260, 2017. © 2015 Society of Plastics Engineers