Monodispersed silica (SiO2) nano- and microparticles can be fabricated by the sol-gel process. For device fabrication, precise formation of composite particles with a homogeneous and facile arrangement that form well-ordered, close-packed arrays is important. In this study, formation of electrostatically assembled SiO2–SiO2 composite particles with excellent homogeneity in arrangement was first demonstrated using sol-gel-derived monodispersed SiO2 particles with average particles sizes of 200 nm and 16 µm. Formation of two- and three-dimensionally, close-packed arrays by electrophoresis-induced stimulation with direct-current and alternating-current electric fields was achieved for the first time using these electrostatically assembled SiO2–SiO2 composite particles. Detailed morphological observation by scanning electron microscopy revealed that the structure of the SiO2–SiO2 composite particles remained intact even after electrophoretic stimulation. The feasibility of obtaining well-ordered arrays of electrostatically assembled sol–gel-derived SiO2–SiO2 composite particles is important for further development of sol-gel-related technology in various applications, such as advanced composites and optical devices.