Owing to the brittleness of the body-centered cubic (BCC) structure and lack of self-lubrication, plasma-sprayed AlCoCrFeNi high-entropy alloy (HEA) coatings undergo severe abrasive wear, resulting in high friction and wear. In this study, the substrate surface temperature was increased (800 °C) to promote the phase transition from BCC to ductile FCC during spraying. As a result, the prepared AlCoCrFeNi HEA coating contained BCC and FCC phases, exhibiting a higher adhesive strength, lower friction coefficient and wear rate at room temperature (RT)–800 °C. In addition, the elevated substrate surface temperature enabled the transition of the low-temperature stable phase α-Bi2O3 to the high-temperature stable phase δ-Bi2O3. δ-Bi2O3 promoted the formation of low shear strength planes owing to its low interaction parameter and defect-fluorite structure with 25 % anionic vacancies similar to that of the Magnéli phase, which facilitated friction reduction in a wide temperature range. This study confirms that δ-Bi2O3 can effectively improve the anti-wear performance of the AlCoCrFeNi-Bi2O3 coating at RT, 200, 600 and 800 °C. However, at 400 °C, the low melting point and soft nature of the Bi2O3 weakened the mechanical strength of the coating and inhibited the construction of a solid and tough tribo-layer, resulting in a relatively high wear rate for AlCoCrFeNi-Bi2O3 coating. At 800 °C specifically, under the thermal coupling effect, δ-Bi2O3 migrated and aggregated on the worn surface with the oxidation product Al2O3 of the AlCoCrFeNi HEA matrix, and jointly promoted the formation of a compact and smooth tribo-layer with lubricating capability, which not only effectively reduced friction but also inhibited wear.