A new cationic poly(3,4‐ethylenedioxythiophene)–DNA composite (P(EDOT‐N)‐DNA) has been prepared by in situ chemical oxidative polymerization of EDOT‐N monomer in the presence of salmon DNA as template. Scanning electron microscopy shows that the P(EDOT‐N)–DNA composite forms a porous pattern with a high surface area that is favorable for ion diffusion throughout the materials, which leads to improved capacitive activity. The P(EDOT‐N)–DNA composite exhibits superior capacitance behavior as well as good charge–discharge reversibility. The P(EDOT‐N)–DNA composite shows low cytotoxicity to living cells even at a concentration of 300 mg · L−1. The good biocompatibility of P(EDOT‐N)–DNA imparts good potential as an environmentally friendly electrode material for energy storage devices, even in a biological environment owing to the combination of DNA with conjugated polymers.
