We report the synthesis and supercapacitive properties of novel poly(2,3,4a, 9a-tetrahydro[ 1,4] dioxino[2,3-b] thieno[3,4-e][1,4] dioxine) (pTDTD) and poly(7-butyl-3,4a, 7,9a-tetrahydro- 2H-[1,4] dioxino[2',3': 5,6][1,4] dioxino[2,3-c] pyrrole) (pTDDP) as redox-active electrode materials for supercapacitor applications. At first, new thiophene and pyrrole monomers containing of fused two 1,4-dioxane rings were successfully synthesized and their conducting polymers were prepared electrochemically on a stainless steel (SS) electrode. Symmetric and asymmetric solid state pseudocapacitor devices were fabricated in order to evaluate supercapacitive performances of newly designed pTDTD and pTDDP. The SS electrodes modified with pTDTD and pTDDP were used as an anode material against pEDOT coated SS cathode in asymmetric devices and as both anode and cathode material in symmetric devices. Capacitive behaviors and performances of the devices were tested by cyclic voltammetry (CV), galvanostatic charge/discharge (GCD) and electrochemical impedance spectroscopy (EIS) techniques. In symmetric devices, pTDTD provided a specific capacitance of 260 F/g and specific energy of 288Wh/kg, while the pTDDP was found to be not a suitable redox-active electrode material for pseudocapacitor applications. (C) 2013 Elsevier B.V. All rights reserved.