High-entropy alloys (HEAs) with high hardness are promising materials for advanced industrial manufacturing. In this study, the AlCrFeNiV HEA was designed and successfully prepared using a plasma instantaneous process. The hardness test showed that AlCrFeNiV had a high hardness of 1076 ± 15 HV, which was much higher than those reported in the literature. The microstructure of AlCrFeNiV was composed of two different types of body-centered cubic (BCC) structures, BCC1 (Al, Cr, Fe, and Ni) and BCC2 (enriched V and Cr). A mixture of different BCC systems produced solution strengthening, which was responsible for the superior hardness. Moreover, the reciprocating sliding wear behavior of HEA against Al₂O₃ balls under dry and lubricated conditions at ambient temperature was investigated. The wear rates of AlCrFeNiV against Al₂O₃ under dry wear and lubrication were 17.2 × 10⁻⁵ mm³ N⁻¹·m⁻¹ and 12.4 × 10⁻⁵ mm³N⁻¹·m⁻¹, respectively, which were of the same order of magnitude as the wear rates of BCC HEAs. Regardless of the dry wear or wear with lubrication, the wear mechanism of the HEA was abrasive and delamination wear.