Modification of titanium via surface-initiated atom transfer radical polymerization (ATRP) was carried out. The surface of the titanium foil was activated initially by a silane coupling agent containing the ATRP initiator, benzyl chloride. Well-defined polymer brushes of poly(ethylene glycol) methacrylate (PEGMA), (2-dimethylamino)ethyl methacrylate (DMAEMA), and 2,3,4,5,6-pentafluorostyrene (PFS) were successfully tethered on the silane-coupled titanium surface via surface-initiated ATRP of the prospective monomers. Diblock copolymer brushes consisting of PEGMA and DMAEMA blocks were obtained by using the initial homopolymer brushes as the macroinitiators for the ATRP of the second monomer. They provided direct evidence to the dormant character of the graft chain ends. The chemical composition of the functionalized titanium surfaces was characterized by X-ray photoelectron spectroscopy (XPS). The changes in surface hydrophilicity and hydrophobicity as a result of surface graft polymerization were characterized by static water contact angle measurements. The metal-polymer hybrids so obtained were stable to hydrolysis in the pH range of 2-12.