Surfaces unable-to-be-irradiated are those that could not be directly exposed to UV irradiation because of their irregular structure or instability under UV irradiation. It is difficult to conduct surface photografting on these kinds of surfaces with conventional photografting methods. Here, a novel one-step surface photografting method is introduced, by which some monomers were smoothly grafted on the surface of polymer substrates located in a region out of the reach of UV radiation. The mechanism is that the photochemical reaction is separated into three events, absorbing UV light in one place, then transporting light energy to another place, and reacting there; in other words, the conventional photochemical reaction is separated by space and time, and the key point is that the substrate does not need to be exposed to UV irradiation. The occurrence of grafting polymerization was proved by UV-vis, ATR-IR, SEM, XPS, and water contact angle measurements. (c) 2006 Wiley Periodicals, Inc.