The creation of new alloys with improved qualities has become essential in modern industries for high-performance materials. This work’s main objective is to use vacuum arc melting (VAM) to synthesize two different high-entropy alloys (HEAs): AlCrFeNiCu and AlCrFeNiCo. The mechanical properties, phase composition, grain boundaries, and alloy composition of the HEAs were studied. The predominant crystal structure, the Body-Centred Cubic (BCC) phase was obtained for both alloys. Significantly, the Co-containing HEA showed a smaller particle size than the Cu-containing HEA, which led to a 14.21% increase in microhardness. It indicates that the Co-based HEA will likely perform better than the Cu-based HEA in applications prone to abrasion, and indentation, and requiring high hardness levels based on the observed microstructure and hardness parameters. According to wear surface morphology studies, main effects analysis and ANOVA show that increasing loads and sliding distances increase wear rate, whereas sliding velocity has less effect. The best wear rate-reducing parameters are 10 N, 0.5 m/s, and 500 m for Cu-containing HEAs, and the same can be predicted using regression analysis. The study categorizes the intricate worn surface structure by describing different surface properties and wear mechanisms, such as grooves, delamination, adhesive wear, and pitting.