The invention relates to a simple preparation method of Fe (ferrous), Co (cobalt) and N (nitrogen) three-element co-doping three-dimensional graphene with catalytic synergistic effect. The preparation method comprises the following steps of enabling soluble fully-aromatic PBI (polybenzimidazole) to react with a ferrous salt and cobalt salt mixing solution; firstly, preparing a complex of PBI, ferrous ions and cobalt ions; adding a nanometer template agent into the reaction mixing liquid; regularly arranging the complex at the surface of the template agent; pyrolyzing, removing a template, and the like, so as to prepare the Fe-Co-N three-element co-doping three-dimensional graphene. The PBI is selected from fully-aromatic macromolecules, such as ABPBI and mPBI, and the viscosity average molecular weigh is 20,000 to 40,000; the molar ratio of ferrous salt and cobalt salt is 1:2 to 2:1; the mass ratio of PBI and ferrous salt and cobalt salt mixture is 1:2 to 2:1; the template agent is selected from nanometer magnesium oxide, ferric oxide and ferric hydroxide nanoparticles; the particle size of the template agent is 5 to 50nm; the mass ratio of PBI and template agent is 3:1 to 1:3; the pyrolysis temperature is 700 to 1000 DEG C; the Fe-Co-N three-element co-doping three-dimensional graphene can be applied to the fields of redox reaction catalysts, fuel batteries, metal air battery redox catalysts, water electrolysis separation catalysts, supercapacitors and the like.