Monodispersed chitosan/silica core-shell microspheres-supported Pd catalysts were prepared by a simple and affordable microfluidic device. Merely 5 mg of supported Pd catalyst (1 wt %) showed superior capability in Sonogashira coupling reactions between various aryl iodides and terminal alkynes in a mild environment (ligand-free, copper-free, amine-free, water-ethanol as solvent at 65 degrees C) even after eight cycles of use. These novel porous composite microspheres provide a new carrier to reduce the loading, enhance the activity, and increase the stability of noble metal catalyst.