Recently, widespread concern has been aroused on environmentally friendly materials. In this article, barium phytate (Pa-Ba) was prepared by the reaction of phytic acid with barium carbonate in deionized water, which was used to blend with intumescent flame retardant (IFR) as a flame retardant and was added to epoxy resin (EP). Afterward, the chemical structure and thermal stability of Pa-Ba were characterized by Fourier transform infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA), respectively. On this basis, the flammability and flame retardancy of EP composites were researched. It is shown that EP/14IFR/2Ba composite has the highest limiting oxygen index (LOI) value of 30.7%. Moreover, the peak heat release rate (PHRR) of EP/14IFR/2Ba decreases by 69.13% compared with pure EP. SEM and Raman spectra reveal the carbonization quality of EP/14IFR/2Ba is better than that of other composites. The results prove that Pa-Ba can cooperate with IFR to improve the flame retardancy of EP, reducing the addition amount of IFR in EP, thus expanding the application range of EP. In conclusion, adding Pa-Ba to IFR is a more environmentally friendly and efficient method compared with others.