Two novel structures of adamantane-modified benzoxazines were synthesized from 4-(1-adamantyl)-phenol through the incorporation of adamantane as a pendant group into the polybenzoxazine backbone. Both H-1-NMR and Fourier transform infrared spectra were used to characterize these structures. The rigid structure of the adamantane tended to hinder the chain mobility (boat anchor effect) and substantially enhanced the thermal properties, including the glass-transition temperature and decomposition temperature, especially for poly(6-adamantyl-3-methyl-3,4-dihydro-2H-1,3-benzoxazine). In the poly(6-adamantyl-3-phenyl-3,4-dihydro-2H-1,3-benzoxazine) system, however, the opposite result for the glass-transition temperature was observed and it was interpreted as lower crosslinking density. The phenyl group was bulkier than the methyl group, and the movement of the molecular chain was hindered between bridging points during the curing process; this resulted in a lower crosslinking density and a lower glass-transition temperature than those of poly(6-adamantyl-3-methyl-3,4-dihydro-2H-1,3-benzoxazine). (C) 2004 Wiley Periodicals, Inc.