Comminution of coal to ultrafine sizes by high-pressure waterjet coupled with cavitation cell provides a novel method for preparation of coal-water fuels for next generation, near-zero emission electric power generation. To establish the fundamental performance of the waterjet mill, the effects of the operating pressure and stand-off distance were comprehensively investigated using a high ash bituminous coal. The comminution products were evaluated in terms of the particle size, particle size distribution, and surface area change. The experimental results indicated that the waterjet-mediated comminution of coal was strongly affected by all these operating parameters. Higher operating pressure led to finer products, while the efficiency of the waterjet mill in terms of particle size strongly depended on the stand-off distance. This research provides a deeper insight into the high-pressure waterjet for coal comminution and a basis for process parameter optimization.