A　photo-Fenton　catalyst　Fe‑carbon　nitride　(g-C3N4)/reduced　graphene　oxide　(rGO)　(labeled　as　FNGO)　was　prepared　via　two-step　calcination　thermal　polymerization.　rGO　as　a　carrier　of　Fe-g-C3N4　accelerated　the　charge　transfer　and　improved　the　reduction　of　Fe　(III)　as　compared　those　of　the　binary　Fe-g-C3N4　catalyst.　The　FNGO　catalyst　maintained　a　high　surface　area　of　264.7　m2/g　and　its　charge　transfer　rate　was　2.77　times　higher　than　Fe-g-C3N4.　The　decreasing　transient　photocurrent　and　increasing　electrode　resistance　of　FNGO,　Fe-g-C3N4　and　g-C3N4　confirm　the　positive　synergistic　effect　of　Fe[sbnd]N　coordination　and　rGO　in　charge　transfer.　Under　the　synergistic　of　visible　light　irradiation　and　H2O2,　the　excellent　degradation　performance　of　FNGO　towards　rhodamine　B　was　achieved　(95.3　%　removal)　at　Fe-doping　content　of　10　wt%,　rGO　loading　content　of　0.5　%　and　H2O2　addition　of　1.5　mM.　Hydroxyl　radicals　played　a　dominant　role　in　the　photocatalysis-Fenton　system,　which　was　related　to　the　coordination　of　Fe[sbnd]N,　the　carrier　off-domain　of　rGO,　and　the　Fe　(III)/Fe　(II)　cycle　promoted　by　photogenerated　electron　and　superoxide　radicals.　The　FNGO　had　a　high　stability,　a　wide　pH　adaptation　(3–　11)　and　a　low　Fe-leaching.　This　novel　ternary　light-driven　photo-Fenton　catalyst　of　FNGO　enabled　efficient　decontamination　during　advanced　treatment　of　wastewater.　©　2023