Congo red doped poly (3,4-ethylene dioxythiophene)/graphene oxide (GO/CR-PEDOT) composite was prepared by simple chemical oxidation method, where Congo red doped poly (3,4-ethylene dioxythiophene) (CR-PEDOT) evenly and stably coated on the surface of graphene oxide (GO) under the guidance and connection of congo red (CR), respectively. Therefore, GO with a large specific surface area could bring into full play its function as a supporting skeleton to decrease the degree of volume expansion and shrinkage of GO/CR-PEDOT composite in charge/discharge process and improve its specific capacitance and cycle stability. The results showed that the maximum specific capacitance of GO/CR-PEDOT composite was up to 227 F/g when the feeding mass ratio of GO to 3,4-ethylene dioxythiophene was 1:1, which was 110% higher than that of poly (3,4-ethylene dioxythiophene) (PEDOT), and the capacitance retention was 92.3 % after 10,000 cycles. Furthermore, a model of asymmetric supercapacitor was fabricated by using GO/CR-PEDOT composite as positive material, activated carbon as negative material and 1 mol/L Na2SO4 as electrolyte, which exhibited that the energy density was as high as 14.4 Wh/kg when the power density was 996 W/kg and still achieved 9.11 Wh/kg at a high power density of 7999 W/kg.