As a poly (3,4-ethylenedioxythiophene) doped with poly (styrene sulfonate), PEDOT:PSS is well known for its conductive polymer in a field of organic electronics. PEDOT:PSS can be widely operated as electronics under low temperature conditions; however, the layer can be easily damaged by high temperature conditions, while in fabrication or in the operation of electronics. Therefore, enhancing the thermal stability of PEDOT:PSS can be a novel strategy for both fabrication and operating varieties. Herein, PEDOT:PSS is the surface-treated with tannic acid to increase the thermal stability. A large number of phenols in tannic acid not only provide UV absorption ability, but also thermal stability. Therefore, tannic-treated PEDOT:PSS film sustained 150 °C for 96 h because of its initial conductivity. Moreover, surface properties and its bonding nature was further examined to show that the tannic acid does not damage the electrical and film properties. The method can be widely used in the field of organic electronics, especially because of its high stability and the high performance of the devices.