A novel curing and flame retardant agent (PEPA-TMA), has been synthesized via 2,6,7- trioxa-l-phosphabicyclo-[2.2.2]-octane-4-methanol (PEPA) to react with trimellitic anhydride (TMA). PEPA-TMA and melamine cyanurate (MCA) were combined into epoxy resin (EP) to obtain halogen-free flame retardant epoxy resin composites. The flame retardancy was characterized by limited oxygen index (LOI) and UL-94 testing. The results showed that the incorporation of PEPA-TMA/MCA into EP can improve the flame retardancy relatively. The thermal degradation process was characterized using thermogravimetric analysis/infrared spectrometry (TGA-FTIR). The formed volatilized products on thermal degradation of flame retarded epoxy resin (EP) systems indicated that the volatilized products are mainly phosphine (PH3), carbon dioxide (CO2), water (H2O) and aromatic compounds. The char yield was 33.7% at 800°C. The morphologies of formed residue chars were observed by scanning electron microscopy (SEM) demonstrating that the most effective amount of phosphorus is 2.5wt%. The flame retarded mechanism was studied by TGA-FTIR and Energy-dispersive X-ray spectroscopy (EDS) coupled with the analysis of the char residues.