AbstractIn this work, FR‐PNX, an alkylphosphate oligomer was introduced into rigid polyurethane foam (RPUF) to fabricate FR‐PNX/RPUF composites. The flame retardancy, thermal stability, and combustion properties of composites were investigated by limiting oxygen index (LOI), thermogravimetric (TG), microcalorimetry (MCC), scanning electron microscopy (SEM), et al. The flame retardancy tests demonstrated that the incorporation of 50 phr of FR‐PNX yielded composites that the highest LOI of 23.6 vol% and achieved a V‐0 rating in the UL‐94 test. TG results indicated that FR‐PNX promoted the decomposition of FR‐RPUF in the process, but enhanced the high‐temperature stability of the composites. MCC analyses revealed that the addition of FR‐PNX suppressed the heat release during combustion, and FR‐PNX50/RPUF exhibited the lowest total heat release of 17.3 MJ/m2, a 35% reduction compared to the pure sample. Moreover, the peak heat release rate was decreased to 83.1 W/g, representing a 46.9% reduction compared to pure RPUF. SEM and Raman analyses of the char residue demonstrated that the incorporation of FR‐PNX facilitated the formation of a dense and continuous char layer in the FR‐RPUF, with increased graphitization degree of the char layer, thereby enhancing the composite's fire resistance through the development of a more stable fire barrier.