The role of functionality and rigidity of the amphiphilic dopants on the morphology and electrical property of the polyaniline-clay nanocomposites (PANICNs) were studied by preparing polyaniline (PANI) and PANICNs using five structurally different amphiphilic dopants having backbone—phenyl, naphthyl, alicyclic, and alkyl groups. Effect of the size and functionality of the dopant on the extent of intercalation/exfoliation, morphology, thermal stability, and phase transitions were studied. PANICNs exhibited different morphologies such as nano/micro granules, rods, nanotubes, aggregated layers/clusters, and rice grain for PANICN-2,6-naphthalene sulphonic acid, PANICN-para-toluene sulphonic acid, PANICN-stearic acid, PANICN-dodecyl benzene sulphonic acid, and PANICN-camphor sulphonic acid, respectively. X-ray diffraction, Fourier transform infrared, and scanning electron microscopic studies showed that the self-assembled nano/microstured aggregates were formed by the combined effect of many noncovalent interactions such as phenyl–phenyl stacking, hydrogen bonding, ion–dipole interaction, π–π stacking, and electrostatic layer-by-layer self-assembling. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009.