High molecular weight poly(phenylene sulfide-phenyleneamine) (PPSA, M-n = 1.5 x 10(5)) was synthesized via a poly(sulfonium) cation through an acid-induced polycondensation reaction of [4-(methylsulfinyl)phenyl]phenylamine. To our best knowledge, the new polymer represents the first hybrid structure of poly(phenylene sulfide) (PPS) and polyaniline (PAni). In contrast to these two intensively studied polymers, PPSA exhibits a high solubility in solvents, such as THF, DMF, DMSO, and NMP. DSC and X-ray studies revealed the completely amorphous structure of PPSA, which cannot even be influenced by annealing the polymer at temperatures above the glass transition. Furthermore, electronic properties were studied by cyclic voltammetry, and preliminary doping experiments for elucidating the electrical conductivity were carried out.