A coupling reaction is performed between polymeric nanoparticles and microparticles via the nucleophilic substitution of pendent beta-diketone groups with benzyl chloride. The coupling reaction results in the formation of hierarchical particles, through the nanoparticles being covalently linked onto the microparticles. The coupling reaction is tracked by TEM and SEM, and the formation of covalent CC bonds through the coupling reaction between the polymeric nanoparticles and microparticles is confirmed by solid-state 13C CP-MAS NMR spectroscopy and XPS. The proposed coupling reaction between the nanoparticles and the microparticles is believed to be a promising strategy in particle-surface modification.