In this article, the volume resistivity of polypropylene (PP)/chlorinated polypropylene (CPP)/polyaniline (PANI) composites was detected. The results show that the volume resistivity of PP/CPP/PANI composites decreases with increasing CPP content, and there exists a minimum volume resistivity. The relationship between volume resistivity of the PP/CPP/PANI composites and CPP content can be explained by Fourier-transform infrared spectra (FTIR). Effects of CPP on the formation of the intermolecular and innermolecular hydrogen-bond in the PP/CPP/PANI composites were carefully investigated by FTIR. An iterative least-squares computer program was adopted to obtain the best FTIR fit curves of the PP/CPP/PANI composites by varying the wavenumber (nu), width at half-height (w(1/2)), and area (S) of several bands. The obtained semiquantitative results illuminate that the intermolecular and innermolecular H-bonded interaction of the PANI-DBSA is weakened by the introduction of CPP; the interactional strength between PANI-DBSA and CPP increases with increasing CIPP content, and there exists a maximum, which is favorable to disperse well PANI-DBSA in PP/CPP/PANI composites and improve the conductive property of the PP/CPP/PANI composites. POLYM. ENG. SCI., 49:462-470, 2009. (c) 2008 Society of Plastics Engineers