We have prepared a series of poly(methyl methacrylate) (PMMA)-based copolymers through free radical copolymerization of methyl methacrylate in the presence of 2-ureido-4[1H]-pyrimidinone methyl methacrylate (UPyMA). The glass transition temperature was increased with the increase of UPyMA contents in PMMA copolymers due to strong self-complementary multiple hydrogen bonding interactions of UPy moiety. The Fourier transform infrared and solid-state NMR spectroscopic analyses provided positive evidence for the presence of multiple hydrogen bonds interaction of UPy moiety. Furthermore, the proton spin-lattice relaxation time in the rotating frame [T-1 rho(H)] for the PMMA copolymers had a single value that was less than pure PMMA, indicating the smaller domain sizes in PMMA copolymers. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 123: 3275-3282, 2012