Hybrid dual-phase coatings composed of an A356 aluminum alloy modified by plasma electrolytic oxidation (PEO) and burnished with graphite-MoS2-Sb2O3 chameleon solid lubricant powders have been produced. The PEO layer provides high hardness and load support while the solid lubricant powders reduce friction. These hybrid coatings were tribotested against steel and silicon nitride counterparts in air from 25 °C to 300 °C and using variable contact loads. The open porosity and surface roughness of the PEO layers were reduced considerably by the burnishing process. Polishing of the PEO surfaces prior to burnishing significantly reduced the resulting coefficient of friction (COF) of the hybrid coating. In-situ Raman spectroscopy revealed the chemical stability of the dual phase coatings at temperatures up to 300 °C with no signs of oxidation or reduction of the chameleon components. COF values ranged from 0.2 at room temperature down to 0.02 at 300 °C. The observed low friction values were attributed to the synergism between PEO and chameleon layers that promote defect healing and adaptive behavior of the coating. Top view scanning electron microscopy (SEM) and cross-sectional transmission electron microscopy (TEM) confirmed that the thermo-mechanical stimulus caused the chameleon coating to fill the voids in the PEO layer. In-situ Raman spectroscopy revealed that the lubricating phases, i.e. MoS2 and graphite, were protected from oxidation by the porous PEO structure. These lubricious phases formed a transfer film in the wear tracks and the counterpart bodies as a result of the contact pressure (up to 1.4 GPa) and thermal energy, which led to an order of magnitude reduction in the COF at high temperatures. The low shear strength of MoS2 and graphite and the good adhesion and integration of the chameleon coating with the PEO sublayer due to high contact pressures during sliding were responsible for the ultra-low friction behavior of the composite coating.