The heterogeneous assembly of colloidal polymer particles on the nano- and microstructures of a metal is a versatile platform for adjusting the mechanical and electrical properties simultaneously. The assemblies of silver (Ag) microrods and flower-like zinc oxide (ZnO) microparticles with poly(methyl methacrylate) (PMMA) nanospheres are presented to prepare advanced composite materials. PMMA nanoparticles are prepared via the emulsion polymerization technique using a microfluidic preparation step in the presence of cationic surfactant. The surface charge of PMMA particles determines the binding interaction strength with inorganic constituents. Ag microrods and ZnO microparticles are prepared in a batch and in a continuous flow process, respectively. The assembling process can be explained by a particle-particle binding process due to the electrostatic interaction for both types of nanoassemblies. The observed binding pattern reveals certain lateral mobility of the small polymer particles at the surface of larger metal particle. The particle ratios in the nanoassemblies can be tuned over a wide range by changing the reaction parameters.