We report the facile preparation of polyaniline-decorated chemically reduced graphene oxide hybrid as electrode materials for pseudocapacitive supercapacitors. The hybridization process of commercially available polyaniline on chemically reduced graphene oxide is based on totally noncovalent approach using π–π interaction between π-rich polyaniline and 2D π-conjugated chemically reduced graphene oxide. Hybrid of polyaniline and chemically reduced graphene oxide demonstrated enhanced specific capacitance of 320F/g at 1.0A/g and superior pseudocapacitive cycling performance (retention of 55% after 1000 cycles) compared with pristine polyaniline (138F/g at 1.0A/g, retention of 31% after 1000 cycles) through the synergic effects of electrically conducting and mechanically robust graphene with high surface area in the hybrid.