In this work, colloidal aggregates, such as higher-order clusters with polyhedral geometry, supraparticles with intermediate packing ordering, different inner structured supraballs with face-centered cubic ordering were produced through self-assembly of different quantities of monodisperse silica nanospheres in water-in-oil emulsion droplets which were formed by ultrasonic dispersion of silica nanospheres suspension into different solvents. The structure evolution of colloidal aggregates as a function of the number of constituent silica nanospheres was studied in this article. It was found that the inner structures of colloidal aggregates would be changed with increasing of the number of constituent silica nanospheres in different solvents. In the case of n-octanol being as solvent, the supraparticles were the transition structure for higher-order clusters into supraballs with hollow structure, while in silicone oil, the supraparticles were the transition structure for higher-order clusters into solid structured supraballs. (C) 2017 Elsevier Inc. All rights reserved.