Epoxy　resin　(EP)　is　one　of　the　most　versatile　polymers.　Nonetheless,　its　inherent　flammability　and　brittleness　severely　limit　its　broad　development.　Moreover,　existing　additives　make　it　difficult　to　meet　the　dual　requirements　of　flame　retardancy　and　toughening.　Herein,　a　novel　P/Fe/Si-doped　porphyrin　derivative　(MTPD-Fe@SiO2)　with　nano-cauliflower　structure　was　synthesized　to　develop　advanced　EP　composites.　MTPD-Fe@SiO2　exhibited　good　dispersion　in　EP　matrix,　which　is　attributed　to　the　π-π　interactions　between　the　porphyrin　and　EP　chains,　as　well　as　the　mechanical　interlocking　of　nano-cauliflower　rough　structure.　Moreover,　when　5　%　of　MTPD-Fe@SiO2　was　incorporated,　the　tensile　and　flexural　strengths　of　EP　composites　were　increased　by　48.1　%　and　63.5　%,　respectively,　showing　excellent　toughening　properties.　Additionally,　the　maximum　thermal　degradation　rate　of　EP/5　%　MTPD-Fe@SiO2　was　significantly　reduced,　indicating　its　superior　thermal　stability.　Notably,　compared　with　pure　EP,　the　peak　heat　release　rate　and　the　peak　smoke　production　rate　of　EP/5　%　MTPD-Fe@SiO2　were　decreased　by　36.4　%　and　43.6　%,　while　the　residual　char　and　limiting　oxygen　index　increased　to　30.9　%　and　32.1　%,　respectively.　This　was　ascribed　to　the　catalytic　charring　of　transition　metals　and　phosphates,　the　barrier　effect　of　the　solid　carbon　layer　(Fe4(PO4)2O,　SiO2),　the　trapping　effect　of　phosphorus　radicals　and　the　dilution　effect　of　incombustibles.　This　work　provides　a　viable　approach　to　solving　the　trade-off　between　refractoriness　and　mechanical　performance.　©　2024　Elsevier　Ltd