Owing to the light weight and high energy, the “All-aluminum engine” can reduce fuel consumption and pollutant emissions, showing a great significance in saving resources and protecting the environment, and becoming a research hotspot. However, the aluminum alloy cylinder liners have difficulty withstanding extremely harsh working conditions, such as strong friction and wear, making the engine extremely easy to damage. In this work, Al-25Si wear-resistant coating was deposited by inner hole supersonic plasma spraying technique to improve the wear resistance of the aluminum alloy cylinder liner. The microstructure, phase composition, mechanical properties and tribological properties were tested by SEM, XRD, tribological machine, etc. The results indicated that the coating exhibited an excellent bonding strength of 44.1 MPa, and the average hardness and average friction coefficient of the coating are 267.09 ± 14.85 HV0.2, and 0.20, respectively. The total wear amount, the wear scar width and the wear scar depth of the coating are 2.77 × 10−3 mm3, 654.3 μm and 8.95 μm, respectively, which showed that the coating can significantly improve the tribological properties of the “All-aluminum engine”. The wear mechanism of the coating was mainly interpreted by furrow cutting, extrusion and spalling in two-body abrasive wear, three-body abrasive wear and a small amount of oxidative wear.