The invention discloses a graphene with a porous structure and a preparation method of the graphene. The porous grapheme consists of a single-layer or multi-layer graphene structure unit, the single-layer or multi-layer grapheme structure unit has a pore-shaped structure (pore diameter is 0.1-200 nm) and a large specific surface area (300-2000 m<2>/g), thus the graphene has potential application value in the aspects of super-capacitors, conductive filling materials and the like. The preparation method of the porous grapheme is characterized in that MgO, Mg(OH)2, Al2O3, Al(OH)3, hydrotalcite compounds and/or corresponding calcined products of the substances are used as catalysts, or MgO, Mg(OH)2, Al2O3, Al(OH)3, hydrotalcite compounds and/or corresponding calcined products of the substances are used as carriers so as to further load one or more active components of Fe, Co, Ni and Mo and then the obtained substance is used as the catalyst ( the pore diameter of the catalyst is 1-200 nm, and the specific surface area is 10-300 m<2>/g); and then at the temperature of 300-1000 DEG C, the graphene is prepared by using inert gases such as nitrogen, argon, helium and the like and using a hydrocarbon chemical gas phase deposition method.