A novel micro-fabrication technique for particle assembly has been performed by an electrophoretic deposition (EPD) method using a local electric field in a colloidal suspension generated by a microelectrode. This unique EPD technique was called a “μ-EPD process”. Monodispersed polystyrene microspheres with diameters of 204, 290, and 320 nm were used in this study. A 50 μm Pt wire embedded into a polytetrafluoroethylene tube and an ITO glass slide were employed as the micro-counter electrode and the substrate, respectively. A slow deposition rate in the μ-EPD process was preferable to form a high quality micro-deposit consisting of a three-dimensional periodic polystyrene array. Under the optimized μ-EPD conditions, three-dimensionally ordered polystyrene particles were deposited in front of the micro-counter electrode. This micro-deposit constructed from polystyrene particles with a close-packed structure showed a characteristic optical absorption peak due to Bragg’s law.