The p-NiO/n-TiO2/polyaniline composites were synthesized via in situ polymerization of aniline. The structure and morphology of the composites were characterized by means of X-ray diffraction(XRD), scanning electron microscopy(SEM), Fourier transform infrared spectroscopy(FTIR) and UV-Vis absorption spectroscopy. It was found that the p-n junction p-NiO/n-TiO2 particles were trapped in the polyaniline molecular matrix and the polyaniline was deposited on the surface of the particles to form a kind of flower cluster morphologies. The electrochemical behavior of the polyaniline composites was investigated. The electrochemical reactivity of the polyaniline was influenced by the p-NiO/n-TiO2 particles due to the effect of electron-hole pairs in these p-n junction particles. The reversibility of redox process and current intensity of the polyaniline composites with the changing of potential scan rate were also discussed.