We compare two routes for creating protein adsorption-resistant self-assembled monolayers (SAMs) by chemical modification of silicon surfaces with poly(ethylene oxide) (PEO) oligomeric derivatives. The first route involves the assembly of 2-methyl[(polyethyleneoxy)propyl]trichlorosilane (Cl3SiMPEO) films onto oxidized silicon surfaces (OH-SiO(x)) either by a liquid-phase process at room temperature or by a gas-phase process at 423 K, producing Si-O-Si bonds between the substrate and the organic layer. The second pathway makes use of the assembly of poly(ethylene glycol methyl ether) (MPEG) films onto hydrogen-passivated silicon surfaces (H-Si) using a liquid-phase process at 353 or 423 K, leading to the formation of Si-O-C bonds between the substrate and the organic layer. Structural investigation by X-ray reflectometry (XRR) reveals that the thickness and surface densities of the grafted PEO monolayers strongly depend on experimental conditions such as temperature and grafting time. Atomic force microscopy (AFM) shows that very smooth and homogeneous monolayers can be obtained with average roughnesses close to those measured on the corresponding bare substrates. Finally, the antifouling properties of the modified silicon surfaces were evaluated by X-ray photoelectron spectroscopy (XPS), using a membrane protein (P.69 antigen) as model protein. Both types of PEO monolayers exhibit excellent protein repellency, as soon as the grafting density is equal to or higher than 1.7 chains/nm2.