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The nano-TiO2/unsaturated polyester resin (referred to as nano-TiO2/UPR hereafter) was prepared with the "reaction method", by which a chemical bond generated between nano-TiO2 and UP was inserted in the UP long chain. The performance of the nano-TiO2/UPR was determined by such a new structure. The research results showed that the reactivity of nano-TiO2/UPR is higher than that of UPR. The impact strength and bending strength of nanoTiO2/UPR are greatly enhanced as compared with that of UPR. Thermal resistance and dielectric property of nano-TiO2/UPR are the same as that of UPR.