A straightforward method to synthesize quasi-monodisperse gold microspheres from a commercial gold plating solution is reported. The size and the surface roughness of the obtained particles can easily be tuned. In particular, raspberry-like particles with a high active surface area are obtained. The microspheres are assembled on indium tin oxide (ITO) electrodes using the layer-by-layer technique and the overall electroactive surface area is increased, as characterized by cyclic voltammetry. The as-prepared products were characterized by scanning electron microscopy (SEM), powder X-ray diffraction (XRD), cyclic voltammetry, and light microscopy.