Converting the surface of poly(2-hydroxyethyl methacrylate) (PHEMA) hydrogel into a cell-adhesive surface has been successfully achieved through a method based on atom transfer radical polymerization (ATRP) grafting. Following activation of the surface hydroxyl groups of PHEMA by bromination, surface-initiated ATRP of mono(2-methacryloyloxyethyl) phosphate (MMEP) was conducted in a methanol-water system with Cu(I)Br as catalyst at room temperature. The conversion of PHEMA hydroxyl groups to brominated isobutyryl groups and the occurrence of grafting of PMMEP were confirmed by infrared and X-ray photoelectron spectroscopies. Cell attachment experiments were conducted by culturing human corneal limbal epithelial cells on the PMMEP-grafted PHEMA, and on unmodified PHEMA and tissue culture plastic for comparison. The results showed that the grafted PMMEP was homogeneously distributed, and the phosphate groups appeared to significantly promote the attachment, spreading and growth of cells, at a level comparable to the tissue culture plastic.