A systematic investigation on the volumetric expansion of four benzoxazine systems, which are benzoxazine, benzoxazine/tertiary amine, benzoxazine/organic acid, and benzoxazine/epoxy resin/tertiary amine, was done. By using gravitometric and dilatometric methods, etc., studies on volumetric shrinkage, isothermal cure shrinkage, and density versus cure time plots were done. The cure reactions of these benzoxazines were carried out at 140 and 160degreesC. The results show that all benzoxazine systems exhibit apparent volumetric expansion after polymerization, that is, the densities of monomers are larger than are those of polymers at room temperature. But, meanwhile, they exhibit volumetric shrinkage while curing isothermally. The results also show that the higher the cure temperature is, the larger the cure shrinkage of the benzoxazines will be and that the extent of the cure shrinkage of the benzoxazines with the aid of catalysts is larger than is that of thermal polymerization systems. The reason for this is that, accelerated by catalysts, the polymerization rate become faster and the extent of polymerizatiom becomes larger. It is obvious that catalysts can make a notable impact on the cure reaction of benzoxazines. Therefore, the dimension of the volumetric expansion of benzoxazine is associated with its polymerization mechanism, molecular structure, and extent of polymerization.