During tribological loading of metallic alloys at elevated temperatures, the thermo-mechanical coupling effect can lead to the development of a distinct tribolayer, profoundly influencing their tribological behavior. This study reports on the compositional lamination in the tribolayer during dry sliding wear of a VCoNi multi-principal element alloy at elevated temperatures. As the temperature increases from 25 °C to 600 °C, the alloy exhibits a remarkable 40% reduction in the coefficient of friction and a notable two-order-of-magnitude decrease in wear rate. The compositional lamination at 600 °C reveals a distinct tribolayer comprising a nanocrystalline-amorphous oxide glaze layer, a Ni-rich dealloyed layer, and a plastic deformation layer. Within the oxide glaze layer, three sublayers are identified, each featuring a nanocrystalline-amorphous nanocomposite structure with unique equiaxed nanograins. Specifically, the outermost sublayer comprises Co3O4, the intermediate sublayer contains a mixture of Co3O4 and Ni2V2O7, and the inner sublayer consists of V2O5. This multilayered structure is attributed to significant differences in the chemical affinity for oxygen among the constituent elements and their respective diffusion rates in the oxide scale. Significantly, the tribolayer formed at 600 °C exhibits a remarkable 70% increase in yield strength compared to its formation at 25 °C, correlating with a substantial reduction in wear. These findings present a novel avenue for designing self-adaptive, high-temperature wear-resistant alloys through the in-situ formation of a protective compositionally-laminated tribolayer.