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The performance and durability of high-pressure fuel systems in combustion engines are critical for consistent operation under extreme conditions. High-pressure fuel systems are traditionally lubricated with fuel that is compressed and delivered to the combustion chamber. However, lubrication with fuel presents significant challenges in these systems when used with low-viscosity fuels, leading to increased wear rates, especially in reciprocating contacts. This study delved into the tribological performance of steels of varying alloy content (annealed and hardened variants of AISI-52100, CF2, and D2) against alumina and hard 52100 counterbody materials in ethanol and decane environments. Friction and wear behaviors were evaluated, highlighting the influence of material interactions and environmental factors. Elastohydrodynamic lubrication analysis of the tested systems indicated that ethanol and decane form lubricating films of nanometer-scale thickness, confirming the boundary lubrication regimes of the performed tests. In summary, the tribological behavior trends were similar for alumina and 52100 counterbodies. Even though soft 52100 steel demonstrated low friction, its wear was the largest for both tested environments and counterface materials. Among all the tested materials, hard D2 experienced the lowest wear. 52100 and D2 steels showed opposite friction change behavior when comparing hard and soft samples, with lower friction observed for softer 52100 steel and harder D2 steel. Meanwhile, the wear was lower for harder candidates than for softer ones independent of the environment and counterbody material. Raman spectroscopy analysis of the formed wear tracks indicated the formation of carbon films with larger intensities of characteristic carbon peaks observed for more wear-resistant materials. These results suggest the synergistic effect of hardness and tribochemical activity in reducing the wear of materials.