The nano-CeO2 was synthesized by two-step solid-phase reaction. The image of TEM showed that nano-CeO2 with an average size of about 70 nm. The series of polyaniline/nano-CeO2 composites with different PANi: CeO2 ratios were prepared by in-situ polymerization in the presence of hydrochloric acid (HCl) as dopant by adding nano-CeO2 into the polymerization reaction mixture of aniline. The composites obtained were characterized by FT-IR and UV-vis spectroscopy analysis. The FT-IR spectra of nanocomposites indicate different blue-shifts, attributed to C–N stretching mode for benzenoid unit. The UV-vis spectra of nanocomposites display einstein-shifts compared with PANi at 620nm. The conductivity properties of the composites are also changed compare to the pure PANi. These results suggest that the interactions between the polymer matrix and nanoparticles take place in polyaniline/nano- CeO2 composites.