Poly(ethylene glycol) (PEG)-coupled polyaniline (PANI) film surfaces were prepared by incorporating the chlorinie end-capped methoxy PEG (mPEGCl) of molecular weight of about 2000 onto the emeraldine (EM) base form of PANI via N-alkylation. The microstructure and composition of the mPEG-coupled PANI (mPEG-c-PANI) surfaces were characterized by atomic force microscopy, contact angle measurement and X-ray photoelectron spectroscopy. The concentration of surface-coupled mPEG increased with the increase in concentration of the mPEGCl solution. The mPEG-c-PANI film surfaces exhibited enhanced ability to repel protein adsorption, with only an moderate reduction in their electrical conductivity. The mPEG-c-PANI surface with a high concentration of coupled mPEG also exhibited good resistance towards platelet adhesion.