We have found that a soft, hydrophilic shell is necessary in the formation of three‐dimensional colloidal crystals by polymeric microspheres prepared by surfactant‐free emulsion copolymerization. The core‐shell microspheres contain a hard, hydrophobic polystyrene core and a soft, hydrophilic shell made of polyacrylamide or poly(acrylic acid) (PAA). Dilution of the particles induced a red shift of the diffraction peak. We have found a pH switching effect for the formation of colloidal crystals by the microspheres with a PAA shell. When the carboxylic‐acid groups are protonated, the colloidal crystals lose their order. The same effect is observed when a poor solvent is added to the colloidal crystals formed by the microspheres with a polyacrylamide shell.
