Flame-retardant halogen-free epoxy resin, containing phosphorus and nitrogen atoms in the main chain, was synthesized through the curing of tris(3-(bis(oxiran-2-ylmethyl)amino)phenyl)phosphine oxide (HGE, hexaglycidyl epoxy monomer), starting from tris(3-aminophenyl) phosphine oxide (TAPO) and epichlorohydrin. The molecular structure of HGE with molecular weight 660 was confirmed using Fourier transform infrared, nuclear magnetic resonance, and liquid chromatography–mass spectrometry techniques. Epoxy equivalent weight determined by titration method was 120. The thermal curing behavior of the HGE/TAPO was investigated by differential scanning calorimetry. An intense exotherm due to curing reaction was observed in the temperature range from 123°C to 215°C. The HGE cured with TAPO, 4,4′-diaminodiphenylsulfone (DDS), and 1,5-diaminonaphthalene (DAN) and the thermal behaviors were studied by thermogravimetric analysis. The flame retardancy properties of the HGE/TAPO, DDS, and DAN were evaluated by vertical burning test (UL-94 V). The high performance cured epoxy resins showed high thermal stability and UL-94 V-0 flame retardancy rating.