Composites based on poly(diphenyl amine) (PDPA) and multiwall carbon nanotubes (MWNTs) were prepared by chemical oxidative polymerization through two different approaches: in situ polymerization and intimate mixing. In in situ polymerization, DPA was polymerized in the presence of dispersed MWNTs in sulfuric acid medium for different molar composition ratios of MWNT and DPA. Intimate mixing of synthesized PDPA with MWNT was also used for the preparation of PDPA/MWNT composites. Transmission electron microscopy revealed that the diameter of the tubular structure for the composite was 10-20 nm higher than the diameter of pure MWNT. Scanning electron microscopy provided evidence for the differences in the morphology between the MWNTs and the composites. Raman and Fourier transform IR (FTIR) spectroscopy, thermo-gravimetric analysis, X-ray diffraction, and UV-visible spectroscopy were used to characterize the composites and reveal the differences in the molecular level interactions between the components in the composites. The Raman and FTIR spectral results revealed doping-type molecular interactions and coordinate covalent-type interactions between MWNT and PDPA in the composite prepared by in situ polymerization and intimate mixing, respectively. The backbone structure of PDPA in the composite decomposed at a higher temperature (> 340 degrees C) than the pristine PDPA (similar to 300 degrees C). This behavior also favored the molecular level interactions between MWNT and PDPA in the composite. (c) 2006 Wiley Periodicals, Inc.