Abstract: Chromium steel serves as a common material for sealing rings, with varying mechanical properties across different grades. An imported high-chromium martensitic stainless steel (unknown grade) sealing ring paired with an antimony impregnated graphite seal ring in a petrochemical pump maintained good sealing performance over long-term service. In this study, the investigation of the tribological properties of domestic high-chromium martensitic stainless steels (9Cr18 and 9Cr18MoV) with antimony-impregnated graphite using a multifunctional friction and wear tester provided a basis for the material selection of domestic chromium steel sealing rings. Microscopic morphology and composition analysis techniques, including confocal laser scanning microscope, scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and phase analysis of X-ray diffraction, were employed to investigate the wear mechanism. The results of the reciprocating sliding wear test conducted in a ball-on-flat contact configuration showed that the tribological behavior of 9Cr18MoV was similar to that of the imported high-chromium martensitic stainless steel. Under oil lubrication, the friction coefficient of 9Cr18MoV was stable and slightly lower than that of the imported Cr alloy, with no significant wear traces observed on the worn surfaces of either stainless steel, except for a few shallow scrapes. The friction coefficient of 9Cr18 fluctuated significantly, and its worn surface exhibited obvious plastic deformation. Under dry conditions, the variation in friction coefficient over sliding time and the average friction coefficient of 9Cr18MoV aligned with those for the imported Cr alloy, while 9Cr18 exhibited a longer running-in time and a higher average friction coefficient. Furthermore, friction and wear tests were conducted on the sliding contact between a pin-on-disc, comparing the friction and wear behavior of two domestic stainless steels, 9Cr18 and 9Cr18MoV, under different contact stresses (1.0, 1.5, 2.0, 2.5, 3.0 MPa) and linear velocities (0.4, 0.7, 1.0, 1.3, 1.6 m/s). The results indicated that as contact stress and linear velocity increased, wear traces on both 9Cr18 and 9Cr18MoV surfaces became more pronounced, accompanied by a rise in contact interface temperature. Notably, under the given linear velocities, contact stresses, and lubrication conditions, the 9Cr18MoV surface exhibited a low friction coefficient with minimal fluctuations, slight surface wear, and a smaller temperature rise compared to the 9Cr18 surface. Under oil lubrication, the primary wear mechanism of both stainless steels was abrasive wear, while under dry conditions, wear was dominated by the transfer of counterpart material, accompanied by the oxidation of metallic Sb to form Sb₂O₅ during the transfer process. Upon further analysis, it became evident that the exceptional tribological properties of the 9Cr18MoV were closely linked to its microstructure and chemical composition. The trace elements Mo and V in 9Cr18MoV refined the grains and promoted the precipitation of large-particle carbides at the grain boundaries, thereby enhancing the material’s resistance to deformation and damage, reducing the risk of hard carbide particles detaching during friction and wear, and consequently improving the material’s wear resistance. In summary, 9Cr18MoV had excellent tribological properties, demonstrating great promise for mechanical seal applications.