The methods of preparation and characterization of core-shell poly(styrene-tert-butoxy--vinylbenzyl-polyglycidol) particles arranged in colloidal crystals are described. The particles wereprepared via emulsifier free emulsion copolymerization of styrene and alpha-tert-butoxy-omega-vinylbenzyl-polyglycidol macromonomer in aqueous medium, initiated by potassium persulfate. The individualpolymerizations differed in a way of addition of macromonomer to the polymerization mixture. The parti-cles assemblies were characterized by atomic force microscopy, Secondary Ion Mass Spectrometry (SIMS)and X-ray Photoelectron Spectroscopy (XPS). In-depth distribution of chemical states was determined byXPS combined with argon gas cluster ion sputtering (Ar-GCIB). The morphology of microspheres assem-blies reflected the composition of the entire particles. It was found that the method of macromonomeraddition to the polymerization mixture affects the particles size, surface and overall morphology.