In order to improve the properties of boron-containing phenol-formaldehyde resin (BPFR), the tetrabromo-bisphenol A epoxy resin (TBBPAER) was used to cure BPFR. The curing mechanism, thermal properties and the fire resistance of TBBPAER/BPFR were investigated by fourier transform infrared spectrometer (FTIR), thermal gravimetric analysis (TGA), torsional braid analysis (TBA) and the oxygen index method. The results show, -OH of -C6H4-CH2OH and -C6H4OH reacts with the epoxy group. With the increase in the amount of BPFR, the thermal properties get better. When the additive amount of TBBPAER is 10 wt%, this material has best thermal stability at high temperature and higher temperature of loss bromine. The glass transition temperature (Tg) is 223.2 °C and the LOI is 68.5.