Lignin, an abundant polyphenolic biomass, has excellent carbonization potential, making it highly promising for developing ecofriendly flame retardants. This study combined ammonium polyphosphate (APP) and alkaline lignin (AL) to create a novel core−shell flame retardant, APP@AL. APP@AL was then applied to rigid polyurethane (RPU) foam to improve its flame-retardant performance and interfacial compatibility with the matrix. Results showed that the mean heat release rate and total heat release of flame-retardant RPU foam decreased by 76.8% and 65.9%, reaching 58.61 kW/m 2 and 19.09 kW/m 2 , respectively, along with a significant improvement in smoke suppression, and TSP was decreased to 1.67 m 2 . The flame retardant content for each RPU was 25 wt % of the polymethylene polyphenyl isocyanate. The flame-retardant mechanism was further explained by analyzing the char layer structure and the pyrolysis gasphase products. Moreover, APP@AL enhanced the interfacial compatibility of RPU, as verified by digital image correlation, which demonstrated an improved stress transfer efficiency during compression. Compared with unmodified RPU foam, APP@AL-modified RPU showed a 10.3% increase in compressive strength and a 6.2% reduction in thermal conductivity. This work provided a novel strategy for thermal insulation, reinforcement, and smoke suppression of rigid polyurethane foams.