Covalent organic frameworks (COFs) build via periodic arrangement of organic building blocks are attracting increasing interest in recent times due to the huge scope in their synthesis through a wide range of structural motifs and diversity in their potential applications. Here we report the synthesis of a new porous extended network π-conjugated TFP-NDA-COF via solvothermal Schiff base condensation of 1,3,5-triformylphloroglucinol (TFP) with 1,5-diaminonaphthalene (NDA). The electrochemical study demonstrates that TFP-NDA-COF has the capability of energy storage up to 379 F g−1 at 2 mV s−1 scan rate, 348 F g−1 at 0.5 A g−1 and offer excellent specific capacitance retention of 75% after 8000 charge discharge cycles. High electrochemical performance could be attributed to the π-electronic conjugation along the polymeric 2D layered network and ion conduction inside the porous channel and permanent porosity of the framework. This indicates that the COF reported herein meets the key requirements like energy storage ability and electrochemical stability needed for developing an efficient energy storage device.