In this study, a set of well-defined multiarm star copolymers, hyperbranched poly(ethylenimine)-graft-poly(ethylene glycol) (bPEI-g-PEG) with different PEG grafting ratios were synthesized. The star PEG-based coatings were then prepared by immobilizing the corresponding copolymers onto poly(dopamine) (PDA)-coated substrates. The chemical composition, hydrophilicity, surface topography, and thickness of the coatings were studied by X-ray photoelectron spectroscopy (XPS), water contact angle (WCA), atomic force microscopy (AFM), and variable angle spectroscopic ellipsometry (VASE), respectively. Furthermore, the surface PEG chain density of star PEG-based coating was evaluated quantitatively and compared with that of linear PEG-based coating. Our results showed that the amount of proteins (albumin from bovine serum, fibrinogen, and lysozyme) adsorbed on the star PEG-based coating as measured by surface plasmon resonance (SPR) was found to be dependent on the surface PEG chain density, which was controlled by the polymer incubation concentrations and PEG grafting ratios. Generally, the star-shaped PEG gave the surface with higher PEG chain density than linear ones and the amount of adsorbed proteins decreased with increasing surface PEG chain density. At last, the star PEG-based coating was successfully applied into the capillary inner surface for protein separation by capillary electrophoresis (CE). (C) 2015 Elsevier B.V. All rights reserved.