Poly(furfuryl alcohol) bioresin (PFA) was synthesized and utilized through two distinct alloying strategies. It was crosslinked by a bismaleimide (BMI) via a Diels-Alder (DA) reaction. The novel PFA-BMI polyadduct network was spectrally, thermally, and thermo-mechanically characterized and its thermally repeatable self-healing behavior was visually established. The network showed a high pyrolytic thermostability (char yield 51% at 600 8C). PFA was also used for modification of epoxy-novolac resin (EP). EP hybrid resins containing 5, 10, and 15 wt % of PFA were cured by a polyamine hardener. Despite of different curing mechanisms of the two resins, PFA had no effect on EP curing behavior as revealed by differential scanning calorimetry, which proved homogeneous formation of the thermosets. PFA at the composition of 15 wt % improved tensile properties and toughness of EP, so that it almost doubled tensile modulus and elongation at break. However, PFA slightly deteriorated flexural properties of EP. PFA also decreased T g of EP, with a maximum decrease of 22 8C. Besides, PFA disfavored initial thermostability of EP, but improved its pyrolytic char yield. In conclusion, PFA can be beneficial from smart materials to toughen hybrid epoxy thermosets with potential applications in composites, adhesives, and surface coatings.