The　peroxynitrite/Fe(III)porphyrin　chemical　system　was　established　firstly　to　investigate　the　effects　of　peroxynitrite　on　the　metabolism　of　polycyclic　aromatic　hydrocarbons(PAHs).　By　comparing　the　conversion　ratio　of　benzo[a]pyrene　(B[a]P)　in　four　model　systems　consisting　of　different　iron　porphyrins,　we　found　that　the　peroxynitrite/T(p-CI)PPFeCl　system　showed　the　highest　catalytic　efficiency,　which　conversion　ratio　of　B[a]P　reached　20.71%.　We　also　analyzed　the　metabolites　of　B[a]P　and　pyrene　(PN)　produced　from　this　system　by　HPLC　and　MS　methods,　and　successfully　identified　the　formation　of　nitrobenzo[a]pyrene　and　nitropyrene　which　are　the　special　metabolites　induced　by　peroxynitrite.