Biocopolymers based on vanillin/fufurylamine–biobenzoxazine (V-fa) and epoxide castor oil (ECO), a bioepoxy, were prepared for application as dental fiber-reinforced composite post. The mechanical and thermal properties of the V-fa/ECO biocopolymers were assessed with regard to the influence of ECO content. The addition of the ECO at an amount of 20% by weight into the poly(V-fa) preserved the stiffness, glass transition temperature and thermal stability nearly to the poly(V-fa). Differential scanning calorimetry (DSC) was used to examine the curing kinetics of the V-fa/ECO monomer system with different heating rates. To determine the activation energy (Ea), the experimental data were subjected to the isoconversional methods, namely Flynn–Wall–Ozawa (FWO) and Friedman (FR). The V-fa/ECO monomer mixture showed average Ea values of 105 kJ/mol and 94 kJ/mol. The results derived using the curing reaction model and the experimental data were in good agreement, demonstrating the efficacy of the FWO method for determining the curing kinetics parameters. The simulated mechanical response to external applied loads by finite-element analysis of the tooth model restored with glass fiber-reinforced V-fa/ECO biocopolymer post showed a similar stress field to the tooth model restored with a commercial glass fiber post. Therefore, based on the findings in this work, it is evident that the bio-based benzoxazine/epoxy copolymer possesses a great potential to be used for dental fiber post.Graphical