Palladium nanoparticles based composite electrodes have been fabricated using polyaniline (PA) and nordihydroguaiaretic acid (NDGA). Two types of nano palladium composite films were electrochemically fabricated using electroactive polymer PA and antioxidant NDGA. Both nanocomposite films were found to be electrochemically active and stable in various pH conditions. The surface morphologies of these two films were analyzed using AFM. PA-nano Pd film modified electrodes was employed for oxygen reduction reactions (ORR). Linear sweep voltammetry (LSV) was used to demonstrate the enhanced electrocatalytic activity of PA-nano Pd film modified GCE. Furthermore, chronoamperometric experiments were carried out to investigate the kinetic parameters of oxygen reduction reaction at this type of electrodes. In addition, the NDGA-nano Pd film modified electrodes were employed for the detection of As (III) in pH 7.0 PBS.