We first present an alternative one-step route for constructing a novel polyaniline (PANI)-coated polypyrrole (PPy) composite in an ingenious triple-phase interface system, where PPy and PANI are prepared in individual non-interference interfaces and, in the middle aqueous phase, smaller PANI particles are uniformly coated on the surface of PPy particles, forming a core shell structure. The prepared PPy/PANI composite electrode shows a superior capacitance behavior that is more suitable for supercapacitor application. (C) 2014 Elsevier B.V. All rights reserved.