The　extensive　utilization　of　rigid　polyurethane　foam　(RPUF)　as　construction　insulation　material　has　brought　two　main　troubles　to　our　society:　fire　risks　and　toxic　hazards.　To　reduce　the　fire　hazards　of　RPUF,　a　layered　MoS2　decorated　with　Cu2O　nanoparticles　was　creativity　obtained　by　hydrothermal　technology　and　facile　wet　chemical　treatment　for　reducing　the　toxic　product　formations　of　polyurethane　nanocomposites　during　combustion.　Due　to　the　low　weight　ratio　of　Cu2O　attached　onto　MoS2,　the　resulting　Cu2O-MoS2　hybrid　effectively　prevented　the　MoS2　nanosheets　from　restacking.　However,　the　Cu2O-MoS2-M　hybrid　was　produced　by　increasing　content　of　Cu2O　which　has　the　characteristic　stacked　layer　structure　of　MoS2　.　Reduced　harmful　organic　volatiles　and　the　toxic　gases　(e.g.　a　respective　decrease　of　ca.　28%　and　53%　for　CO　and　NOx　products)　were　obtained　because　of　synergistic　effect　between　the　physical　adsorption　of　MoS2　and　catalysis　action　of　Cu2O.　Notably,　the　addition　of　Cu2O-MoS2　hybrids　led　to　high　char　formation　of　the　RPUF　nanocomposite,　indicating　the　effectively　catalytic　carbonization　property.　In　addition,　the　N-Gas　model　for　predicting　fire　smoke　toxicity　was　developed　and　demonstrated.　Furthermore,　the　research　offers　direct　proofs　of　the　negative　influence　of　the　stacked　MoS2　on　reducing　the　smoke　toxicity　for　RPUF　nanocomposites.