Here, we fabricated an AlCrNiTiV high entropy alloy amorphous film (HEAAF) by co-filter cathode vacuum arc deposition (Co-FCVAD). The systematic experiments demonstrate that excellent mechanical properties and a stable dense microstructure are important contributing factors in a friction-corrosion coupling environment, in which the AlCrNiTiV HEAAF oxidized at 600 °C exhibits optimal tribocorrosion resistance with a minimum Δ open circuit potential (ΔOCP), friction coefficient (COF) and wear rate of 0.015, 0.01 and 2.36 × 10−6 mm−3 N−1•m−1, respectively. Through study of the oxidation behaviour, it is found that the diffusion barrier formed in situ by the Al2O3, NiCr2O4 and Cr2O3 composite inner oxide layer after oxidation at 800 °C can effectively impede the outward diffusion of metal ions and inward diffusion of O ions, but the film shows a deterioration in hardness and a loose microstructure, which are the main failure factors under a friction-corrosion coupling environment. Additionally, the AlCrNiTiV HEAAF shows excellent high-temperature tribological performance under a friction-temperature (600 °C) coupling environment with the lowest COF (0.22) and wear rate values (1.1 × 10−5 mm3 N−1•m−1). However, a brittle oxide film composed of rutile TiO2 on the worn track is found to be responsible for the weak high-temperature tribological performance under a friction-temperature (800 °C) coupling environment.