A novel nanocomposite of palladium nanoclusters/poly(N-acetylaniline) nanorods was electrodeposited on to a glassy carbon electrode by cyclic voltammetry (CV). This electrode, Pd/PAANI/GCE, was characterized by X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), CV and chromoamperometry. It was demonstrated that the ball-shaped Pd nanoclusters were mainly growing on the ends of the nanorods, forming a novel nanocomposite. The preliminary study also demonstrated that the electrode modified with this nanocomposite matrix had high electrocatalytic activity toward 4-e-s oxygen reduction.