A high performance polybenzoxazine derived from bio-based furfurylamine was synthesized in an efficient and straightforward way. For comparison, its petroleum-based analogue was also prepared from 4, 4-diaminodiphenylmethane (DDM). The chemical structures of the precursors were confirmed by Nuclear Magnetic Resonance Spectroscopy (H-1-NMR and C-13-NMR) and Fourier Transform Infrared Spectroscopy (FT-IR). After the curing reaction was investigated by Differential Scanning Calorimetry (DSC) and FT-IR in detail, the thermal and mechanical properties of the cured resins were studied by Dynamic Mechanical Analysis (DMA) and Thermogravimetric Analysis (TGA). Results demonstrated that the polybenzoxazine based on furfurylamine (BZ-F) possessed higher glass transition temperature (270 degrees C) and better thermal stability associated with higher charring ability when compared with the one (BZ-DDM) derived from DDM, which might be attributed to the stronger hydrogen bonding interaction in the BZ-F system and the post-curing reaction on furan ring above 280 degrees C. In this paper, the hydrogen bonding effect on the properties of polybenzoxazine has been especially studied, which might give us a guidance to design and synthesize the polybenzoxazine with high performance. (C) 2017 Elsevier Ltd. All rights reserved.