The flammability of rigid polyurethane foam (RPUF) limits its application. A new type of chitosan phase-change microcapsule (CS/PCM) was successfully prepared by the condensation method with chitosan and gum acacia as the wall material and paraffin as the core material. CS/PCM was introduced into RPUF composite material as filler to improve the thermal and flame-retardant properties of polyurethane. The morphology, structure, thermal properties and flame retardancy of the materials were characterized by scanning electron microscopy (SEM), X-ray diffractometer (XRD), thermogravimetric (TG) analysis, differential scanning calorimetry (DSC) and cone calorimetry. It is found that when the CS/PCM content is 30 wt%, the latent heat of phase transition of RPUF-30 is 12.308 J/g, the limiting oxygen index (LOI) is 26.1% and the fire risk is reduced. The flame-retardant mechanism shows that the barrier effect provided by chitosan plays an important role in effectively blocking the transfer of heat and combustible gas, and improving the flame-retardant property of the composite. This paper provides a new idea for the application of CS/PCM in RPUF.