Herein, we report a novel photocleavable and polymerizable oligopeptide for versatile design of biofunctional polymers. Radical copolymerizations of the peptide with various vinyl monomers successfully produce graft-type peptide-polymer hybrids. The resultant RGDS peptide/PHEMA hybrid film is applied to photolithography, and provides spatially limited location of the bioactive RGDS peptides. Furthermore, such photocleavage of the RGDS-graft chains can also tune cell adhesion to the surface.