Aligned carbon nanotubes (ACNTs) were modified with polypyrrole (PPy) via electropolymerization. Because of the large specific surface area and excellent electrical conductivity of ACNTs, continuous electropolymerization was able to be carried out, forming a thick PPy coating on the ACNTs. The resulting nanocomposite possessed a core-shell structure with ACNTs as the core, PPy as the shell, and nanoparticles of PPy on the top, and displayed high performance supercapacitance properties.