Arrays of oriented poly(3,4-ethylenedioxythiophene) (PEDOT) micro/nanorods are synthesized by electrochemical galvanostatic method at the current density of 1mAcm−2 in the cetyltrimethylammonium bromide (CTAB) aqueous solution whose pH value is 1. The CTAB is used both as the surfactant and the supporting salt in the electrolyte solution. The electrochemical properties of PEDOT films are characterized by cyclic voltammetry and galvanostatic charge/discharge techniques, which indicate that the arrays of oriented PEDOT micro/nanorods can be applied as the electrode materials of supercapacitors. In addition, the cycling performance of PEDOT micro/nanorods is much better than that of traditional PEDOT particles. The effects of the concentration of CTAB, the current density, and pH value of electrolyte solutions on the morphologies and electrochemical properties of PEDOT films are investigated. The mechanism of different morphologies formation is discussed in this study as well.