AbstractN‐Acryloyl‐N′‐4‐tolylurea (ATU) and N‐methacryloyl‐N′‐4‐tolylurea (MTU) were prepared via the reaction of 4‐tolyl isocyanate with acrylamide or methacrylamide. In conjunction with ceric ammonium nitrate (CAN), ATU and MTU promote the rate of acrylamide polymerization. Macromolecules having 4‐tolylureido pendant groups, such as poly(ATU‐co‐EA) and poly(MTU‐co‐EA), were synthesized by radical copolymerization of ATU and MTU with EA (ethyl acrylate), respectively. In the presence of CAN, a graft copolymerization of acrylamide onto the surface of these two copolymer films took place. The grafted copolymer was characterized by means of XPS and SEM and with respect to water absorption.