The invention discloses a graphene and nickel diselenide composite and a preparation method thereof. The preparation method comprises the steps that a reducing agent is mixed with a graphene oxide solution, even stirring is conducted to form a brown solution, the brown solution is added into a stainless steel reaction kettle with a polytetrafluoroethylene liner, and selenium containing matter and nickel containing inorganic salt are filled into the reaction kettle; the reaction kettle is closed to conduct the reaction; after the reaction is conducted, natural cooling is conducted, suction filtration is conducted on a mixture in the reaction kettle, repeated washing and suction filtration are conducted through distilled water and absolute ethyl alcohol, and the product is collected for storing after drying is conducted. According to the prepared graphene and nickel diselenide composite, nickel diselenide nanoparticles are wrapped with the graphene, nickel diselenide is closely combined with graphene sheets, and the composite has larger specific surface area. According to the graphene and nickel diselenide composite and the preparation method thereof, a simple solvothermal method is adopted, reduction of graphene oxide and preparation of the graphene oxide and the nickel diselenide composite are conducted synchronously, the technology is simple, the reaction temperature is low, the cost is low, the preparation method is green and controllable, and the graphene and nickel diselenide composite is suitable for industrial production.