The invention relates to the technical field of preparation and application of carbon materials, in particular to a preparation method of a municipal sludge derived self-doped iron and nitrogen species carbon material electrode and application of the municipal sludge derived self-doped iron and nitrogen species carbon material electrode as a cathode material to electro-Peroxone reaction to degradetoxic organic pollutants. Municipal sludge serves as a carbon material precursor, after one-step pyrolysis, an obtained carbon material is washed, filtered and dried, the carbon material, acetylene black powder and polytetrafluoroethylene dispersion liquid are mixed and dissolved in an ethanol solvent according to a certain proportion, ultrasonic treatment, stirring, drying and pressing are carried out to form a film, a titanium mesh serves as a carrier for compounding, and the electrode is prepared. The material is self-doped with iron and nitrogen species, iron and nitrogen sources do not need to be additionally added, the preparation method is simple, the cost is relatively low, and the obtained product is more environmentally friendly. And when being used as a cathode material in degradation of toxic organic pollutants by an electric-Peroxone reaction, the composite material shows excellent catalytic degradation activity and degradation rate, and the efficiency of the composite material is far higher than that of a common carbon-based material.