These studies demonstrate a new approach of producing multifunctionalized coatings on poly(tetrafluoroethylene) (PTFE) surfaces by covalent attachments of multilayers (CAM) of heparin (HP) and poly(ethylene glycol) (PEG). This process can be universally applied to other covalently bonded species and was facilitated by microwave plasma reactions in the presence of maleic anhydride which, upon ring-opening and hydrolysis, provided covalent attachment of COOH groups to PTFE. These studies showed that alternating layers of PEG and HP can be covalently attached to COOH-PTFE surfaces, and the volume concentration and surface density of PEG and HP on the PTFE surface achieved by the CAM were 7.02-6.04 × 10(-3) g/cm(3) (2.1-1.8 × 10(-7) g/cm(2)) and 9.3-8.7 × 10(-3) g/cm(3) (2.8-2.6 × 10(-7) g/cm(2)), respectively. The CAM process may serve numerous applications when the covalent modification of inert polymeric substrates is required and particularly where the presence of bioactive species for biocompatibility enhancement is desirable.