This paper introduces a stepwise formation method for micro-sized, multilayered core–shell particles comprising an inorganic core, organic inner shell, and inorganic outer shell. A silica core was coated with a polystyrene seed layer, followed by surface seed polymerization with styrene, to afford the inner shell. These particles were then coated with a silica outer shell by a surface sol–gel reaction with tetraethoxysilane. The versatility of this combined surface seed polymerization and sol–gel method is emphasized by the precise control achieved over particle diameter as well as shell thickness and count. Moreover, the organic inner shell can be readily eliminated to afford a single-core-containing micro-capsular structure.