In this study, a simple one-step template-free solution method was developed for the preparation of poly(3,4-ethylenedioxythiophene) (PEDOTs) with different morphologies by adjusting various ratios of oxidant (FeCl3·6H2O) to monomer (3,4-ethylenedioxythiophene (EDOT)). The results from structural analysis showed that the structure of PEDOT was strongly affected by the oxidant/monomer ratio, and the polymerization degree, conjugation length, doping level, and crystallinity of PEDOT decreased with increasing of the oxidant/monomer ratio. The morphological analysis showed that PEDOT prepared from an oxidant/monomer ratio of 3:1 displayed a special coral-like morphology, and the branches of 'coral' would adjoin or grow together with increasing content of oxidant in the reaction medium; consequently, the morphology of PEDOT changed from coral to sheets (at an oxidant/monomer ratio of 9:1). The electrochemical analysis proved that the PEDOT prepared from an oxidant/monomer ratio of 3:1 had the lowest resistance and the highest specific capacitances (174 F/g) at a current density of 1 A/g with a capacity retention rate of 74% over 1,500 cycles, which indicated that the PEDOT with a coral-like morphology could be applied as a promising electrode material for supercapacitors.