Polyurethane coating was designed to give a hydrophobic property on its surface by modifying it with hydroxyl terminated polydimethylsiloxane and then effects of surface hydrophobic tendency, water transport behavior and hence corrosion protectiveness of the modified polyurethane coating were examined using FT-IR/ATR spectroscopy, contact angle measurement and electrochemical impedance test. As results, the surface of polyurethane coating was changed from hydrophilic to hydrophobic property due primarily to a phase separation tendency between polyurethane and modifier by the modification. The phase separation tendency is more appreciable when modified by polydimethylsiloxane with higher content. Water transport behavior of the modified polyurethane coating decreased more in that with higher hydrophobic surface property. The decrease in the impedance modulus ${mid}Z{mid}$ at low frequency region in immersion test for polyurethane coatings was associated with the water transport behavior and surface hydrophobic properties of modified polyurethane coatings. The corrosion protectiveness of the modified polyurethane coated carbon steel generally increased with an increase in the modifier content, confirming that corrosion protectiveness of the modified polyurethane coating is well agreed with its water transport behavior.