Electrodes modified with oppositely charged platinum and gold nanoparticles exhibit electrocatalytic synergy of glucose oxidation. Such a simple method of preparation of bimetallic nanoparticulate films produces an electrode with significant shift of the onset potential as compared to electrodes prepared only from platinum (ca. 0.45 V) or gold (ca. 0.6 V) nanoparticles. The observed effect results from close proximity of the Au and Pt nanoparticles surfaces within the film. The electrode was also characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, powder X-ray diffraction measurements and cyclic voltammetry.