A holistic approach to fabricate a hierarchical electrode that consists of redox-active poly(1,5-diaminonaphthalene), 1,5 PDAN, uniformly and conformally grafted onto a 3D carbon nanotube (CNT-a-CC) electrode is set forth. The CNT-a-CC electrode was formed by direct growth of high-density CNTs on the surface of every individual microfiber, the constituent of activated carbon cloth (a-CC). Owing to the naphthalene backbone, conformal deposition of 1,5 PDAN on carbon surfaces has been readily attained via electropolymerization. This hierarchical platform with open and continuous nanochannels formed by CNTs coupled with excellent electrical connectivity between CNTs and the polymer provides a reproducible platform for electrochemical investigation. According to multiple sample analyses on CNT-a-CC, the gravimetric capacitance of 1,5 PDAN is up to 1250 F/g, and this value can be maintained up to 100 mV/s. Hierarchical organization provides a specific capacitance of 650 F/g at 2 mV/s at a 1,5 PDAN loading of 2.5 mg/cm(2). The conjugated ladder structure of the polymer led to strong pi-pi interactions between the polymer and CNT-a-CC together with mechanically robust CNT-a-CC. A capacitance retention of 94% for 1,5 PDAN has been obtained after 25,000 cycles at 100 mV/s, a significant cycle stability improvement over conventional conductive polymers such as polyaniline. This new lightweight electrode that seamlessly integrates functional species with nanochannel-like CNT-a-CC opens up a new opportunity to harness electrochemical reactions in the 3D carbon electrode for energy storage and electrocatalysis as well as electrochemical sensing.