Tris(2,2'-bipyridine)ruthenium(II) ([Ru(bpy)3]2+) is one of the most extensively studied and used electrochemiluminescent (ECL) compounds owing to its superior properties, which include high sensitivity and stability under moderate conditions in aqueous solution. In this paper we present a simple method for the preparation of [Ru(bpy)3]2+-containing microstructures based on electrostatic assembly. The formation of such microstructures occurs in a single process by direct mixing of aqueous solutions of [Ru(bpy)3]Cl2 and K3[Fe(CN)6] at room temperature. The electrostatic interactions between [Ru(bpy)3]2+ cations and [Fe(CN)6]3- anions cause them to assemble into the resulting microstructures. Both the molar ratio and concentration of reactants were found to have strong influences on the formation of these microstructures. Most importantly, the resulting [Ru(bpy)3]2+-containing microstructures exhibit excellent ECL behavior and, therefore, hold great promise for solid-state ECL detection in capillary electrophoresis (CE) or CE microchips.