The invention discloses a sintering method of cobalt-free tungsten carbide. The sintering method comprises: 1, respectively weighing graphene and nanometer WC powder, uniformly mixing, and drying; and 2, placing the dried graphene and nanometer WC powder mixture into a graphite mold, compacting, sintering at a temperature of 1500-1700 DEG C with a discharge plasma sintering device, carrying out thermal insulation for 5 min, cooling, and taking out the sample. According to the sintering method of the present invention, the high toughness and the high breaking strength of the graphene are utilized to enhance the fracture toughness of the sample; and the graphene is electrically conductive, such that the sintering performance can be changed during the use of the discharge plasma sintering. With the method of the present invention, the sintering temperature is substantially reduced, the sintering time is short, the thermal insulation time is short, and the obtained tungsten carbide has the superfine structure.