Properties of two types of polystyrene microspheres with polyacrolein and polyglycidol components in their surface layers are compared. Microspheres were prepared in batch radical emulsifier-free emulsion copolymerizations of styrene with acrolein and/or α-tert-butoxy-ω-vinylbenzyl-polyglycidol macromonomer (M n = 2700). Polymerizations were initiated with potassium peroxodisulfate, and the ratio of initial concentrations of styrene and initiator was constant. Number average diameters of poly(styrene/acrolein) (P(S/A)) and of poly(styrene/polyglycidol) (P(S/PGL)) particles were in the range of 200 -650 nm and decreased with increasing concentration of acrolein and/or polyglycidol in the polymerizing mixtures. The diameter polydispersity of synthesized particles (D /D w n ) was usually lower than 1.02. X-ray photoelectron spectroscopy for P(S/A) and P(S/PGL) microspheres showed that surface layers of particles were significantly enriched in polyacrolein or polyglycidol segments, surface fractions of which increased with increasing concentration of the more hydrophilic comonomer in the polymerizing mixture. In the case of P(S/A) particles, the maximal fraction of polyacrolein approached 80 mol-%, whereas for P(S/PGL) particles the maximal surface fraction of PGL was 42 mol-%. Human serum albumin was used as a model protein for studies of attachment onto P(S/A) and P(S/PGL) microspheres. It has been found that for both kinds of particles, the maximal surface concentration of attached (adsorbed and/or covalently immobilized) protein decreased with increasing fraction of hydrophilic component in the particle surface layer (polyacrolein or polyglycidol units). In the case of P(S/A) particles, adsorption always accompanied covalent immobilization of proteins. To the contrary, covalent immobilization of proteins onto the P(S/PGL) microspheres proceeded without adsorption of proteins.