An organic solvent soluble and high electrical conductivity, for example, 55.43 S/cm, polyaniline (PANI), was synthesized by a novel method. In this two steps process, a noncovalent approach was initially developed by functionalization of multiwalled carbon nanotubes (MWNTs) using calcium lignosulfonate (LsCa) via self-assembly to result MWNTs-LsCa. Then, the MWNT-LsCa was employed as a template to lead anilinium monomers directly aligned on the surface to start the polymerization of PANI. The noncovalent modification of MWNTs avoided their agglomeration effectively to allow them doped in PANI at the molecular level. The obtained novel PANI/MWNTs-LsCa presented excellent solubility and high conductivity. The recorded scanning electron microscopy photographs revealed that the MWNTs-LsCa was wrapped with PANI chains that caused the crystal orientation improvement. In this article, a related scheme on resulting in the high conductivity of PANI/MWNTs-LsCa was showed and described. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2036-2046, 2009