A facile electrochemical route was applied to prepare polypyrrole (PPy)/anthraquinone sulfonate (AQS)/reduced graphene oxide (r-GO) composite. The as-synthesized composite showed an interconnected porous structure, which is related to the competitive relationship between two dopants. The cyclic voltammograms and electrochemical impedance spectra confirmed that the presence of highly conductive r-GO in PPy matrix ensured an efficient redox reaction obtained for redox-active AQS. As a result, the PPy/AQS/r-GO composite exhibited an enhanced specific capacity of 127.2 mAh g−1 with ca. 100% coulombic efficiency at 0.1 A g−1. Furthermore, the superior rate capability and cycling stability were also observed for PPy/AQS/r-GO, compared to AQS doped PPy. It is possible to adopt this co-dopants system for creating electro-active polymer materials with high capacities that are comparable to that of conventional inorganic intercalation electrode materials.