A phosphine oxide-containing bio-based curing agent was synthesized by addition reaction between furan derivatives and diphenylphosphine oxide. The molecular structure of the as-prepared bio-based curing agent was confirmed by Fourier transform infrared spectroscopy and nuclear magnetic resonance spectroscopy. Dynamic mechanical analysis results indicated that with the increase of bio-based curing agent content, the glass transition temperature of epoxy/bio-based curing agent composites decreased, which was related to the steric effect of diphenylphosphine oxide species that possibly hinder the curing reaction as well as the reduction in the cross-linking density by mono-functional N H. By the addition of 7.5 wt-% bio-based curing agent, the resulting epoxy composite achieved UL-94 V-0 rating, in addition to limiting oxygen index of 32.0 vol-%. With the increase of content for the bio-based curing agent, the peak of heat release rate and total heat release of the composites gradually decreased. The bio-based curing agent promoted the carbonization of the epoxy matrix, leading to higher char yield with good thermal resistance. The high-quality char layer served as an effective barrier to retard the diffusion of decomposition volatiles and oxygen between molten polymers and the flame. This study provides a renewable strategy for fabricating flame retardant and transparent epoxy thermoset.