In the present work, an arrangement of polystyrene (PS) spheres was employed as a pattern for the electrodeposition of nanostructured Prussian blue (PB). The pattern of PS spheres was formed on Indium tin oxide (ITO) glass substrate. The ITO substrate modified by the PS spheres was used as a working electrode for the electrosynthesis of PB. A macroporous PB film constituted by nanoparticles of the compound was obtained after the dissolution of the spheres and was characterized by voltammetric and atomic force microscopy techniques. The electrocatalytic properties of this material were tested in the electrooxidation of hydrazine.