Rigid　polyurethane　foam　(RPUF)　shows　great　application　potential　in　the　fields　of　architecture,　household,　and　transportation　due　to　its　lightweight,　durability,　and　excellent　heat　insulation.　However,　it　remains　challenging　to　construct　flame-retardant　and　impact-resistant　RPUF　composites　with　good　thermal　insulation　through　a　facile　approach.　Herein,　multifunctional　hierarchical　RPUF　composites　were　prepared　by　simple　one-pot　foaming　and　brush-coating　methods.　Due　to　the　hierarchical　structure　and　multifunctional　polyborosiloxane/phytic　acid/polyethylenimine　(PBS/PAP)　coating,　the　as-created　foams　displayed　excellent　fire　safety　and　impact　resistance.　For　instance,　the　peak　of　heat　release　rate　and　total　heat　release　of　the　RPUF　composite　with　the　PBS/PAP　coating　decreased　by　70.1　and　57.0%,　respectively,　relative　to　those　of　pure　RPUF.　Furthermore,　the　composite　showed　good　heat　insulation　and　improved　thermal　stability　performance.　This　work　offers　a　paradigm　for　the　design　of　multifunctional　RPUF　composites　with　outstanding　fire　resistance,　impact　resistance,　and　heat　insulation　properties,　which　represent　prospective　potential　in　safety　protective　materials.　©　2024　American　Chemical　Society.