A series of flame-retardant epoxy resins containing boron and silicon were obtained through a crosslinking reaction, using tris (2-hydroxypropyl) borate (THPB) together with octaaminophenyl POSS(OapPOSS) as the curing agents. The limiting oxygen index (LOI) reached 30.5% when the contents of boron and silicon in the cured system were 1.5% and 0.5%, respectively, indicating that THPB and OapPOSS exhibited good flame retardant effect on epoxy resins (EP). Microscale combustion calorimetry (MCC) results indicated that the peak heat release rate (PHRR) and total heat release (THR) of the cured systems were reduced by 69% and 46%, respectively, compared to those of pure EP. Moreover, the thermal degradation process and flame retardant mechanism of the composites were investigated by TGA, real time FTIR and TG-FTIR. The chemical components of the char residues were explored by XPS. (C) 2012 Elsevier B.V. All rights reserved.