The invention provides a preparation method of a flexible self-supporting three-dimensional 
porous graphene film. The preparation method comprises the following steps: selecting a high molecular 
polymer with low 
thermal stability as a templating agent, blending with 
graphene oxide, performing suction 
filtration to form a film, and then performing high-temperature heat treatment under the protection of 
inert gas, wherein during the high-temperature heat treatment, the 
graphene oxide is reduced into 
graphene, and the high molecular 
polymer with the low 
thermal stability is completely decomposedto leave developed pores, so that the flexible self-supporting three-dimensional 
porous graphene film is obtained;and the thickness of the film can be controlled within the range of 5-100 microns, thepore size is in the range of 5-100 nm, and the specific surface area is 300-1600 m<2> / g. The shape, the size and the 
porosity of the prepared flexible self-supporting three-dimensional 
porous graphene film can be conveniently regulated and controlled through the morphology (such as linear, spherical and columnar), the molecular weight and the dosage of the high molecular 
polymer template. The flexible self-supporting three-dimensional porous graphene film can be applied to the fields of flexible supercapacitors, flexible batteries, 
microelectronics, 
ion adsorption, membrane separation and thelike.