In　this　work,　a　novel,　earth-abundant,　and　environmentally　benign　NaFeSi2O6　catalyst　is　synthesized　by　a　one-step　solvothermal　method　without　the　introduction　of　any　surfactants.　NaFeSi2O6　is　for　the　first　time　applied　to　the　heterogeneous　photo-Fenton　reaction　for　the　degradation　of　RhB　under　visible-light　irradiation　with　long-term　stability　and　a　wide　working　pH　range.　OH　plays　the　most　important　role　in　the　photo-Fenton　process.　Besides,　O-2(-)　and　h(+)　are　also　generated　and　involved　in　this　reaction　simultaneously.　Combining　the　experimental　results　and　theoretical　calculations,　it　can　be　confirmed　that　NaFeSi2O6　can　be　regarded　as　a　promising　catalyst　to　improve　the　efficiency　of　the　heterogeneous　photo-Fenton　reaction.