This study concentrates on the effect of organophilic montmorillonite (OMMT) nanolayers on conductivity, structure, morphology, and mechanical properties of the polypropylene/polyaniline (PP/PANI) composites. The composite was prepared by in situ polymerization of aniline at different composition ratios in the presence of PP powder. The structure and conductivity of ternary PP/PANI/OMMT nanocomposites were compared with those of PP/PANI composites. DC electrical conductivity measurements indicated that electrical conductivity decreased in the presence of OMMT layers. Scanning electron microscopy showed that the surface of ternary nanocomposites have more rough regions. The interaction between PANI and OMMT was confirmed by Fourier transform infrared spectroscopy. The distribution of OMMT layers in the polymer matrix, as an effective parameter on the properties of nanocomposite, was investigated and confirmed using X‐ray diffraction and transmission electron microscopy. The results showed an exfoliated array for OMMT layers in the nanocomposite structure. The shear storage modulus for PP/PANI composites was lower than that for pure PP; however, it was increased for PP/PANI/OMMT nanocomposites. The data from the tensile and izod impact strength showed that the Young's modulus and izod impact strength were increased slightly by the addition of OMMT, whereas the elongation at break was decreased. POLYM. COMPOS., 38:699–707, 2017. © 2015 Society of Plastics Engineers