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A novel benzoxazine-based phenolic resin containing furan groups (PFB) was synthesized via simple two-step reactions and the structure of PFB was confirmed by FTIR and 1 H NMR spectra. Differential scanning calorimetry (DSC) showed that the polybenzoxazine cured from PFB had good heat resistance and lower polymerization temperature compared with that of benzoxazine-based phenolic resins.