Palladium (Pd) nanocatalysts are obtained by electroless deposition of Pd on pre-reduced poly(3,4-ethylenedioxythiophene) (PEDOT) layers doped with either polystyrenesulfonate (PSS) or dodecylsulfate (SDS) ions. The PEDOT-supported Pd catalysts are investigated with respect to formic acid (FA) oxidation in slightly acidic solution under voltammetric and chronoamperometric conditions. Atomic force microscopy (AFM) and Scanning electron microscopy (SEM) studies are carried out before and after exposure to FA. It is established that the dopant used for the synthesis of PEDOT does affect not only the distribution of the Pd nanoparticles on the polymer surface but also the stability of the composites upon electrochemical treatment in the presence of FA. It is found that PEDOT-PSS undergoes structural rearrangement, and significant loss of the Pd catalyst is observed. In comparison, PEDOT-SDS is more resistant to FA exposure since aggregated Pd nanoparticles are providing additional stability of the polymer structure.