Poly(ethylene oxide) (PEO), a biomedically important polymer, has been synthesized using a novel liquid-free initiated chemical vapor deposition (iCVD) via a ring-opening cationic polymerization mechanism. In addition, a grafting scheme was used to graft polymerize PEO onto amine-terminated surfaces. FTIR, NMR, and XPS showed a stoichiometric match to linear PEO homopolymer. In addition, XPS confirmed the graft polymerization of PEO to amine anchors on silicon with a high graft density. XPS and GPC were used to measure independently the grafted polymer molecular weight that also showed a narrow weight distribution. The grafted iCVD PEO surfaces were effective in minimizing nonspecific protein adsorption using a fluorescently labeled bovine serum albumin assay.