A novel graphene-coated nanocrystalline ceramic particle, iron-based composite inoculant was developed in this study to optimize the as-cast microstructure and mechanical properties of W18Cr4V high-speed steel (HSS). The effects of the composite inoculant on the microstructure, crystal structure, and mechanical properties of HSS were analyzed using transmission electron microscopy, scanning electron microscopy, energy dispersive spectroscopy, and X-ray diffraction. The (002-) and (020) crystal planes of the Fe3C and Cr7C3 phases, respectively, were collinear at two points in the reciprocal space, indicating a coherent relationship between the Fe3C and Cr7C3 phases in the tempered modified HSS. This contributed to an improved non-uniform nucleation rate and refining of the HSS grains. The mechanical properties of the modified steel exhibited a general improvement. Specifically, the modification treatment enhanced the hardness of HSS from HRC 63.2 to 66.4 and the impact toughness by 48.3%.