The effect of the microstructure of siliconized graphite on tribological properties is investigated by using a high-temperature and high-pressure water-lubricated tribometer on a self-mated ring-on-ring configuration under an applied load of 500–1500 N with a spindle speed of 100–5000 rpm in both 90 °C (5 MPa) and 25 °C (1 MPa) water environments, respectively. The Stribeck curves measurement and continuous wear tests are performed and analyzed in both water environments. The wear behaviors of the graphite, SiC, and free-silicon phases in siliconized graphite are demonstrated to explore the wear mechanism. The larger wear depths of a low-worn surface roughness on the three phases contribute to the boundary lubrication. The shallower wear depths are observed on the SiC and Si phases under the mixed lubrication, corresponding to partial contact wear of surface asperities. The wavy surface of the SiC phase and uniform flow-oriented striae of the Si phase are attributed to hydrodynamic lubrication, caused by full water film scouring the worn surface. Finally, an integrated evaluation method of G duty parameters is successfully used to identify the lubrication regimes of siliconized graphite from the boundary, mixed, to hydrodynamic lubrications for a water-lubricated thrust bearing application in the main coolant pump of a nuclear power plant.