Currently, the effect of the choice of counter ions on the structure and thermoelectric properties of electrochemically polymerized poly(3,4-ethylenedioxythiophene) (PEDOT) films has attracted much attention. Among the reported polymer films, PEDOT:poly(styrene) Sulfonate) (PSS), PEDOT: Tosylate (Tos), PEDOT: Perchloric acid (ClO4) and PEDOT: Trifluoromethanesulfonate (OTf) have been extensively studied. This paper comprehensively analyzes the application of different types of counter ions on the thermoelectric properties of PEDOT films, and focuses on the different process methods of PEDOT:PSS and PEDOT:Tos to improve the thermoelectric properties. PEDOT:PSS films have high conductivity, water treatment and thermal properties It has the characteristics of high stability, and the thermoelectric performance is effectively improved by secondary doping, chemical de-doping and continuous treatment, but PSS has the limitation of hydrophilicity; Tos is hydrophobic, and PEDOT:Tos film can effectively balance the competition The relationship between Baker coefficient and electrical conductivity; other films such as PEDOT:ClO4 and PEDOT:OTf also play a certain role in promoting the thermoelectric performance. Finally, the development and practical application of counterion-polymerized PEDOT films as flexible thermoelectric devices and wearable electronics are prospected. It has a certain reference value for further research on new counter ion polymerization.