This manuscript reports a facile strategy for the modification of polyethylene, a widely used biomaterial, with a thin non-biofouling coating that can act as a platform to introduce biochemical cues to control and direct, e.g., cell adhesion and proliferation. The non-biofouling coating is produced, following a two-step strategy involving photobromination of the polyethylene substrate followed by surface-initiated ATRP of poly(ethylene glycol) methacrylate. The resulting coatings, which are referred to as polymer brushes, are robust and withstand prolonged exposure to aqueous ethanol and phosphate buffered saline and also do not show any signs of detachment or degradation in the in vivo studies over a period of 10 d. Functionalization of these polymer brush coatings with extracellular matrix derived peptide sequences, promotes adhesion and spreading of endothelial cells.