A new monomer, 2-methylene-7-oxabicyclo [2.2.1]heptane (IV) was synthesized via four steps. Its structure was confirmed by IR, H-1-NMR, and C-13-NMR spectra as well as elementary analysis. Free radical polymerization and copolymerization of IV were investigated. No homopolymer was obtained due to the effect of allyl inhibition. When IV copolymerized with electron-donor monomers, such as vinyl acetate and styrene, IV acted as inhibitor for the polymerization of vinyl acetate, but could not inhibit the polymerization of styrene. However, the copolymers of IV with electron-accepting monomers, such as methyl methacrylate, acrylonitrile, or maleic anhydride (MA) were obtained. The contents of IV in the copolymers increased as e values of electron-accepting monomers increased. Strictly alternating copolymer was obtained only in the case of MA and IV. The thermal properties of copolymers were investigated.