Abstract: A super-flexible high thermal conductive graphene film and a preparation method thereof are provided. The graphene film is obtained from ultra large homogeeous graphene sheets through processes of solution film-forming, chemical reduction, high temperature reduction, high pressure suppression and so on. The graphene film has an intensity in a range of 1.93 to 2.11 g/cm3, is formed by overlapping planar oriented graphene sheets with an average size of more than 100 ?m with each other through ?-? conjugate action, and comprises 1 to 4 layers of graphene sheets which have few defects. The graphene film can be repeatedly bent for 1200 times or more, with elongation at break of 12-18%, electric conductivity of 8000-10600 S/cm, thermal conductivity of 1800-2600 W/mK, and can be used as a highly flexible thermal conductive device.