In this work, we report a facile strategy to anchor CdTe nanocrystals onto synchronously synthesized polymer for the fabrication of luminescent hollow poly(3-methacryloxypropyltrimethoxysilane) (PMPTS)/CdTe composite colloids. Firstly, glutathione-coated CdTe nanocrystals with green fluorescence were synthesized in an aqueous solution. Dithiothreitol was then introduced into the solution as co-ligand and cross-linker to bridge CdTe and prospective polymer. Subsequently, MPTS monomers and light initiator in toluene solution were added into the CdTe aqueous solution under sonication to form a semi-stable emulsion. Finally, the emulsion was light irradiated to prepare PMPTS colloids and simultaneously graft CdTe nanocrystals onto these colloids through thiol-ene click chemistry. This facile route allows the polymer synthesis and its functionalization with inorganic nanoparticles in one step, potentially leading to practical applications for building diverse hybrid structures.