A composite of a core-shell structured nanowires with ZnO as a core and conductive poly(3,4-ethylenedioxythiophene) (PEDOT) as a shell was prepared. At first, the hexagonal ZnO nanowires, with diameter of about 80-100 nm and length 4-5 mu m, were fabricated by hydrothermal synthesis process. Then a thick layer of poly(trifluoroethyl methacrylate)-block-poly(sodium styrene sulfonate) (PTFEMA-b-PSSNa) was grafted from the surface of ZnO nanowires via atom transfer free radical polymerization. At last, with the ZnO@PTFEMA-b-PSSNa as a template and the PSSNa chain as the counterion dopant, PEDOT was precipitated onto the surface of the template to form the composite of ZnO@PEDOT/PSSNa. With the evaluation of the EDOT polymerization, the thickness of the PEDOT layer increased steadily. However, as the ratio of EDOT/ZnO was greater than 1:2, the ZnO nanowires templates were dissolved at last and then PEDOT particles were produced due to increasing of the acidity during the oxidation polymerization of EDOT. In this case, the product was the mixture of the nanotubes and particles of PEDOT/PPSNa. The electrochemical capacitances of the composites with different structures were investigated with cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy techniques with three-electrode cell configuration. The maximum specific capacitance of ZnO@PEDOT electrode can reach 101.34 F/g at 20 mV/s. (C) 2016 Elsevier B.V. All rights reserved.