A new approach is proposed to biocatalytical synthesis of a thin homogeneous layer of conducting polyaniline (PANI) on the surface of MWCNTs using the laccase Trametes hirsuta. Aniline dimer, an enhancer of laccase-catalyzed aniline polymerization, has been adsorbed on MWCNTs. Phytic acid has been used as acidic dopant and gelator. The PANI/MWCNT composite has a core shell structure and shows a high specific capacitance of 554 F g⁻¹ and long-term cycling stability. The approach enables the production of nanostructured composite conducting hydrogel.