A series of polyaniline/vermiculite nanocomposites was synthesized. The interlayer space of vermiculite was initially increased by the insertion of dioctadecyl dimethyl ammonium bromide, and then the aniline monomers were inserted into the interlayer space of vermiculite replacing dioctadecyl dimethyl ammonium cations. The polyaniline/vermiculite nanocomposites materials were prepared via in situ polymerization of the aniline monomers in the interlayer space of vermiculite. The as-synthesized polyaniline/vermiculite nanocomposite materials were characterized by X-ray diffraction analysis, infrared spectroscopy, and electrical conductivity measurement. The results indicated that the vermiculite was peeled off into the polyaniline. The introduction of vermiculite nanosheets showed a beneficial effect on the electrical conductivity of polyaniline.