Abstract: | This work outlines an interesting approach to bioepoxy resins from sustainable 2,5‐bis((oxiran‐2‐ylmethoxy)methyl)furan (BOF). The 3,3′‐diamino diphenyl‐sulfone (33DDS) and 4,4′‐diamino diphenyl‐sulfone (44DDS) are employed as hardeners. For comparison, petro‐based networks from diglycidyl ether of bisphenol A (DGEBA) are developed as well. The systematic analyses suggest that the BOF/DDS networks show higher crosslink densities and mechanical properties than DGEBA/DDS thermosets. Remarkably, an attractive multilayer tubular microstructure is fabricated in the BOF/44DDS thermosets, and it greatly enhances the mechanical performance. Apart from that, BOF/DDS composites exhibit excellent flame retardancy. Especially, for BOF/44DDS, the self‐extinguishment happens in 7 s. The fire retardant mechanism confirms that a low heat release rate and heat release capacity as well as a compact char layer occur in the pyrolysis of BOF/DDS. Thus, the BOF/DDS exhibits superior performance over its DGEBA counterparts and meets a wide variety of requirements in engineering. |