Free-standing conductive films are important for the application in organic electronics. However, PEDOT as one of the most promising CPs is difficult to be prepared into free-standing paper. Herein, a novel EDOT derivative, 1,6-bis((2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy)hexane (BEDTH), was synthesized and easily electrodeposited into free-standing flexible conducting poly(1,6-bis((2,3-dihydrothieno[3,4-b] [1,4]dioxin-2-yl)methoxy)hexane) (PBEDTH) in CH2Cl2 containing 0.1 M Bu4NBF4. The free-standing PBEDTH films with the conductivity of 0.11 S cm(-1) were characterized by FT-IR, UV-vis, SEM, TG, dynamic mechanical analysis and electrochemical method, respectively. Electrochemical results indicated that the specific capacitance of PBEDTH film was 40.8 Fg(-1) at the current density of 0.5 A g(-1) in ionic liquid BmimBF(4) with the cycling capacitance retention of 86.7% after 5000 cycles. Additionally, the thermoelectric property of free-standing flexible PBEDTH film was also studied, showing the Seebeck coefficient was 37.2 mu VK-1 and the power factor was 0.015 mu WK-2 m(-1) at 300 K. Although the capacitive and thermoelectric performance is not satisfactory, the free-standing flexible PBEDTH films will still be promising in the areas of energies and sensors in the true sense. (C) 2016 Elsevier Ltd. All rights reserved.