Polyethylene oxide (PEO) has been widely used in biomedical fields. The antibiofouling property of the PEO-modified surface has been extensively investigated but is far from being fully understood. A series of PEOs with narrowly distributed molecular weight (M-w), synthesized with the technique of high vacuum anionic polymerization, have been successfully grafted onto the surface of silicon wafers. The power-law relationship between the thickness of the monolayer versus the M-w of the grafted PEO shows a scaling of 0.3, indicating compact condensing of the chains. The static contact angles show higher hydrophobicity for the layer of PEO with higher 4, which can be attributed to the closely packed conformation of the chains with high density. The frequency shift of the contact resonance indicates that the Young's modulus decreases and the loss factor increases with the increase in the M-w, of PEO and the thickness of the PEO layers. Dielectric spectroscopy of bare or PEO-grafted wafers in the aqueous solutions reveals an interfacial polarization, which results from compositional and structural changes in the interface layer and depends on temperatures and salt concentrations. At a given grafting density, the PEO chains are swollen in pure water, demonstrating hydrophilic behavior, whereas they collapse in salt solutions, showing hydrophobic characteristics.