Glass fiber post based on the new polymeric material, polybenzoxazine, is prepared and the effects of glass fiber contents on mechanical and thermal properties are evaluated. The mechanical response to externally applied loads of tooth restored with glass fiber-reinforced polybenzoxazine composite posts is also simulated by finite element analysis of a tridimensional model and compared with the response to that of a natural tooth. The reinforcing of glass fiber can help improve the mechanical and thermal properties of the polybenzoxazine influenced by the interfacial adhesion between the glass fiber and polybenzoxazine matrix, except for the relatively high mechanical property of the glass fiber. The mechanical data, i.e., elastic modulus under flexure load or flexural modulus by three-point bending test of the glass fiber-reinforced polybenzoxazine composites are agreed with the elastic modulus of dentin and then used in the finite element model. The restoration using the glass fiber-reinforced polybenzoxazine composite post provided the maximum von Mises equivalent stress at the cervical third area of the endodontically treated tooth model as similarly observed in the natural tooth. In addition, the maximum von Mises equivalent stress of the tooth restored with the glass fiber-reinforced polybenzoxazine composite post is also quietly like that of the natural tooth. The finding of this work provided the essential properties of the glass fiber-reinforced polybenzoxazine composite for dental restorations and appliances.