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Rigid polyurethane foams (RPUFs) are widely used in many fields, but they are easy to burn and produce a lot of smoke, which seriously endangers the safety of people’s lives and property. In this study, tetraethyl(1,5–bis(bis(2–hydroxypropyl)amino)pentane–1,5–diyl)bis(phosphonate) (TBPBP), as a phosphorus–nitrogen–containing reactive–type flame retardant, was successfully synthesized and employed to enhance the flame retardancy of RPUFs, and silica aerogel (SA) powder was utilized to reduce harmful fumes. Castor oil–based rigid polyurethane foam containing SA powder and TBPBP was named RPUF–T45@SA20. Compared with neat RPUF, the obtained RPUF–T45@SA20 greatly improved with the compressive strength properties and the LOI value increased by 93.64% and 44.27%, respectively, and reached the V–0 rank of UL–94 testing. The total heat release (THR) and total smoke production (TSP) of RPUF–T45@SA20 were, respectively, reduced by 44.66% and 51.89% compared to those of the neat RPUF. A possible flame–retardant mechanism of RPUF–T45@SA20 was also proposed. This study suggested that RPUF incorporated with TBPBP and SA powder is a prosperous potential composite for fire and smoke safety as a building insulation material.