We report an alternative strategy for fabricating nanocrystal-loaded photonic crystals with a polymerizable macromonomer via catalytic chain-transfer polymerization (CCTP) in which CoBF acted as a chain-transfer agent (CTAs). First, monodisperse, functionalized PS-co-PMAA microspheres with polystyrene (PS) cores and poly(methacrylic acid) (PMAA) shells were controllably prepared using styrene and the as-prepared PMAA macromonomer by surfactant-free emulsion polymerization. Then Cd0.4Zn0.6S nanocrystals capped with as-prepared PMAA macromonomer were synthesized by an in situ growth method. Finally, Cd0.4Zn0.6S nanocrystal-loaded PS-co-PMAA microspheres hybrids were obtained through simply mixing an aqueous solution of PS-co-PMAA microspheres with an aqueous solution of Cd0.4Zn0.6S nanocrystals in the appropriate proportions; the multianchor -COOH groups on the surface of core shell PS-co-PMAA microspheres favor incorporation with Cd0.4Zn0.6S nanocrystals. Scanning electron microscopy (SEM) images confirm that PS-co-PMAA microspheres are uniformly surrounded by Cd0.4Zn0.6S nanocrystals. In addition, discrete electronic and photonic states can be combined both with PS-co-PMAA photonic crystals and fluorescent semiconductor Cd0.4Zn0.6S,S nanocrystals.