The interest in thermogalvanic cells (TGCs) has grown because it is a candidate technology for harvesting electricity from natural and waste heat. However, the cost of TGCs has a major component due to the use of the platinum electrode. Here, we investigate new alternative electrode material based on conducting polymers, more especially poly(3,4-ethylenedioxythiophene)-tosylate (PEDOT-Tos) together with the ferro/ferricyanide redox electrolyte. The power generated by the PEDOT-Tos based TGCs increases with the conducting polymer thickness/multilayer and reaches values similar to the flat platinum electrode based TGCs. The physics and chemistry behind this exciting result as well as the identification of the limiting phenomena are investigated by various electrochemical techniques. Furthermore, a preliminary study is provided for the stability of the PEDOT-Tos based TGCs.