Monodisperse colloids have been prepared efficiently by copolymerization of methyl methacrylate and fluorescent first- and second-generation poly(phenylenevinylene) dendrons under surfactant-free emulsion polymerization conditions The copolymers were characterized by UV-vis and fluorescence spectroscopy and size exclusion chromatography. Transmission electron microscopy revealed that the copolymers were microspheres with smooth surfaces and narrow dispersity The bead diameter could be varied by changing the monomer/water ratio The materials could be crystallized to give polymer opal photonic crystals The emission was not affected by the periodic structure because of the large spectral distance between the emission and the pseudogap position (C) 2010 Wiley Periodicals, Inc J Polym Sci Part A Polym Chem 48 2659-2665, 2010