A novel fire-retardant epoxy thermoset, containing boron polyol complex, was prepared and characterised. The fire-retardant additive was a stoichiometric mixture of boric acid and glycerol. Flame retardancy of the epoxy resin was improved by the formation of stable char layer that protected the underlying epoxy from further burning. Phonon transport through the polymer matrix via hydrogen bonding was identified. The hydrogen bonding acted as a thermal bridge for intermolecular phonon transport to gain improved thermal conductivity resulting early char formation. The hydrogen bonding between the complex and the epoxy matrix was demonstrated using Fourier Transform Infrared Spectroscopy. The phonon transport and a high degree of graphitization was confirmed using Raman Spectroscopy. Thermogravimetric analysis was used for polymer decomposition to confirm a char yield of over 20%. Reaction to fire test revealed enhancement in fire retardancy and self-extinguishing properties of the blend compared to the neat epoxy. Cone calorimetry testing confirmed decreased peak heat release rate and total smoke production by the effect of boron compound in the epoxy matrix. Hydrogen bonding, formation of thick stable layer of char at the polymer surface, and a blowing out effect caused by pyrolytic gases escaping to the gaseous phase, were attributed to the improved fire retardancy. This research may find applications in thermal insulation material of electronic circuit boards, coating in aerospace materials, as well as building and construction industries.