Herein, we report a photoinitiated RAFT dispersion polymerization for the preparation of highly monodisperse poly(glycidyl methacrylate) (PGMA) microspheres at room temperature. Fast polymerization rates were achieved, with near quantitative yields within 2 h of UV irradiation. The effect of reaction conditions (e.g., stabilizer concentration, monomer concentration and solvent composition) on particle morphologies was studied in detail. Amine-functionalized PGMA microspheres were prepared by treating PGMA microspheres with ethylene diamine (EDA) at 70 degrees C, and the obtained product was characterized by FT-IR and XPS. Such amine-functionalized PGMA microspheres were able to stabilize oil-in-water Pickering emulsions. Covalently cross-linked colloidosomes were formed by cross-linking primary amino groups on the particle surface using (tolylene 2,4-diisocyanate-terminated poly(propylene glycol) (PPG-TDI) as a cross-linker. Amine-functionalized PGMA microspheres were also employed as templates for the synthesis of PGMA/gold (Au) hybrid microspheres and large gold nanoplates.