A method for chemically modifying a surface with grafted monolayers of initiator groups, which can be used for a “living” free radical photopolymerization, is described. By using “living” free radical polymerizations, we were able to control the length of the grafted polymer chains and therefore the layer thickness up to ∼100 nm. Also, single-layer grafted block copolymers were obtained by subsequent polymerizations of styrene and methyl methacrylate monomers. The surface-grafted polymer and block copolymer layers were evidenced by direct imaging methods (transmission and scanning electron microscopy) and by indirect surface characterization methods (contact angle measurements, SFM, XPS, and IR). The ability to control the thickness of the grafted polymer as well as the synthesis of a grafted block copolymer layer in a well-defined manner affirms the “living” character of the surface-initiated free radical photopolymerization.