Environment can impact the wear behavior of metals and alloys substantially. The tribological properties of Al0.6CoCrFeNi high-entropy alloys (HEAs) were investigated in ambient air, deionized water, simulated acid rain, and simulated seawater conditions at frequencies of 2–5 Hz. The as-cast alloy was composed of simple face-centered cubic and body-centered cubic phases. The wear rate of the as-cast HEA in the ambient air condition was significantly higher than that in the liquid environment. The wear resistance in seawater was superior to that in ambient air, deionized water, and acid rain. Both the friction coefficient and wear rate in seawater were the lowest due to the formation of oxidation film, lubrication, and corrosion action in solution. The dominant wear mechanism in the ambient air condition and deionized water was abrasive wear, delamination wear, and oxidative wear. By contrast, the wear mechanism in acid rain and seawater was mainly corrosion wear, adhesive wear, abrasive wear, and oxidative wear.