Titanium and its alloys represent a major class of materials employed in orthopedic and dental clinical applications. Although titanium-based implants can function effectively for a decade, the long-term clinical success of these devices is limited by implant loosening and wear, especially in younger patients. [1,2] Considerable efforts have focused on implant surface technologies, such as designing rough, porous coatings for bone ingrowth, and bone-bonding ceramic coatings to promote integration into the surrounding bone and thereby enhance mechanical interlock. [1,3,4] However, slow rates of osseointegration, particularly in clinically challenging cases, currently restrict these approaches. Biomimetic coatings, focusing on the presentation of biologically active molecules within a protein adsorption-resistant background, have recently emerged as a promising strategy to enhance osseointegration.[5]Self-assembled monolayers (SAMs) have been explored as a method to control biologically related surface properties such as cell adhesion. [6][7][8][9][10] For example, we have previously demonstrated control over protein adsorption and cell adhesion and function by modification of oligo(ethylene glycol)-substituted alkanethiol monolayers on gold with specific peptide sequences from adhesion proteins. [11][12][13] However, SAMs on gold and silver substrates suffer from long-term instability and loss of bioresistance, and there are severe limitations to the application of robust noble-metal coatings on biomedical materials. [6][7][8][9] To overcome these shortcomings, several groups have concentrated on the engineering of polymeric films on titaniumand silicon-based surfaces to promote robust bioresistance. [14][15][16][17] For instance, adsorption of end-functionalized poly(ethylene glycol) (PEG) onto titanium metal (i.e., a "grafting-to" approach to prepare polymer brushes) affords resistance to protein adsorption.[10] More recently, a "graftingfrom" approach was developed based on surface-initiated atom-transfer radical polymerization (SI-ATRP) of oligo(ethylene glycol)methacrylate (OEGMA) on gold modified with a thiol monolayer of an a-bromo ester initiator. An extensive study of the properties of these brushes was carried out as a function of polymerization time and the surface density of initiator. This afforded the ability to control the thickness of the poly(OEGMA) film and demonstrated the resistance of these surfaces to cell adhesion. [9,16,18] To build on these findings and to explore the development of stable surface modifications of titanium, we set out to establish routes to prepare protein-adsorption-resistant polymer brushes that can be modified with peptide sequences that direct cell adhesion. We describe an approach to modify the surface of titanium with dense polymer brushes of poly(OEGMA) that resist protein adsorption and cell attachment. Furthermore, conversion of the hydroxyl end groups of the oligo(ethylene glycol) (OEG) side chains to 4-nitrophenyl carbonate groups allows for tethering of bioacti...