Polyaniline salts are prepared by doping of polyaniline base with different Bronsted acids (H2SO4, HNO3 and H3PO4), organic acid -p-toluene sulfonic acid (PTSA) and Iodine (I-2). Polyaniline complexes are also prepared using Lewis acids (BF3, AlCl3 and SnCl2). Polyaniline salts and polyaniline complexes are characterized by physical, electrical and spectral methods. Polyaniline salts and polyaniline complexes are used as catalyst for the first time in bisindole synthesis. Bisindole (3,3'-bis(indolyl) phenylmethane) is obtained in excellent yields with simple and more environmental benign procedure. The use of polyaniline catalysts are feasible because of their easy preparation, easy handling, stability, easy recovery, reusability, good activity and eco-friendly.