Polyaniline (PANI) molecular composites were synthesized by chemical oxidative polymerization of the aniline and aniline dimer, N-phenyl-1,4-phenylendiamine, in the presence of a macrocycle, calix[8]arene p-octasulfonic acid (C8S), using ammonium peroxidisulfate as oxidant. The macrocycle has acted both as acid dopant and surfactant to obtain processable PANI-ES. The PANI/calix[8]arene p-octasulfonic acid composite was also obtained by a simple doping of PANI emeraldine base form with calix[8]arene sulfonic acid. The structure of materials was confirmed by Fourier transform infrared, UV-vis and nuclear magnetic resonance spectroscopy. All synthesized composite materials are amorphous and soluble in chloroform, dimethylsulfoxide, NMP, showing excellent solution-processing properties combined with electrical conductivity. Cyclic voltammetry evidenced a good electroactivity for the composite films. Dielectric properties (dielectric constant and dielectric losses) were determined and are comparable with those of other PANI/ionic acid polymer composites. Preliminary studies have evidenced a high dielectric constant (10(4) at 100 Hz) and electrical conductivity of 6 x 10(-3) S/cm for PANI composites. From sulfur elemental analysis of the PANI/calixarene, it results that the content in macrocycle is similar to 30% (weight). (C) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 127: 2796-2802, 2013