Poly(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methanol)/carbon fiber composite material (PDHDM/CF) was prepared via a simple electrodeposition method. The CF core and the PDHDM shell formed a 3-D PDHDM/CF core/shell structure composite. The PDHDM/CF was characterized by FT-IR spectroscopy, UV-vis spectra, SEM, cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectroscope techniques. Compared with the PDHDM deposited on glass carbon electrode (PDHDM/GC), PDHDM/CF exhibited a remarkable specific capacitance of 280 F g(-1) at a scan rate of 10 mV s(-1), which was nearly three times that of the PDHDM/GC. The specific capacitance of assembled symmetric super-capacitor based on PDHDM/CF reached 27.35 F g(-1) at 0.5 A g(-1) and the energy density was 6.38 Wh kg(-1) at a power density of 3.9 kW kg(-1). These results indicated that the PDHDM/CF was a promising electrode material for the flexible supercapacitors application. (C) 2015 Elsevier B.V. All rights reserved.