The flame-retardant rigid polyurethane (PU) foams with hexa-phenoxy-cyclotriphosphazene/expandable graphite (HPCP/EG) were prepared through box-foaming in our laboratoiy. The flame retardancy of PU foams was characterized using the limiting oxygen index and cone calorimeter. The results show that the incorporation of HPCP into the PU foams containing EG enhanced flame retardancy. The main degradation process of HPCP in PU foams was investigated by pyrolysis gas chromatography/mass spectroscopy. HPCP during combustion generated phenoxyl and PO2 free radicals, which could quench the flammable free radicals produced by the matrix and hamper the free radical chain reaction of combustion. This observation shows that HPCP produced a gas-phase flame-retardant effect in this specimen. Additionally, micro-morphology, elemental composition and content of residual char of the flame-retardant PU foams after the cone calorimeter test were also characterized using scanning electron microscope and energy dispersive X-ray microanalyser. The results exhibit that the partial phosphorus from HPCP remained in the residual char, and HPCP significantly enhanced the strength and compatibility of the char layer formed by the PU foams containing EG. These results indicate the important function of HPCP in condensed phase. Thus, HPCP exhibited gas-phase and condensed-phase flame-retardant effects on the PU/EG foams. (C) 2013 Elsevier Ltd. All rights reserved.