Different pi-conjugated sulfonate templates, including dodecylbenzenesulfonate (DBS), 2-naphthalenesulfonate (NAS), N, N'-bis(2,6-diisopropylphenyl)-perylenediimide-1,6,7,12-tetraoxyphenylsulfonate (PTS), as well as auxiliary assistance by graphene (Gra) and multi-walled carbon nanotube (MWCNT), have been utilized to investigate the polymerization behavior of 3,4-ethylenedioxythiophene (EDOT) and the influence on the corresponding morphologies and properties. PEDOT has been self-polymerized with obviously agglomeration without template. Isolated PEDOT grains with coiled shape have been formed by DBS template polymerization. More crystalline and conductive PEDOT with quinoid-conformation and ordered arrangement has been developed by utilizing template with novel pi conjugated sulfonate (PTS). Most prominently, the obtained conductive PEDOT: MWCNT shows continuous interpenetrating network structure with more extended PEDOT and well-dispersed MWCNT due to pi-pi interaction of PEDOT with noncovalent functionalized MWCNT by electron-deficient conjugated sulfonate. Furthermore, a high specific capacitance of 199 F g(-1) at current density of 0.5 A g(-1) for PEDOT: MWCNT has also been demonstrated successfully for owning potential applications in supercapacitors. (C) 2017 Elsevier Ltd. All rights reserved.