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CoCrFeMoNi high entropy alloys (HEAs) exhibit several promising characteristics for potential applications of high temperature coating. In this study, metastable intermetallic phases and their thermal stability of high-entropy alloy CoCrFeMo_0.85Ni were investigated via thermal and microstructural analyses. Solidus and liquidus temperatures of CoCrFeMo_0.85Ni were determined by differential thermal analysis as 1323 °C and 1331 °C, respectively. Phase transitions also occur at 800 °C and 1212 °C during heating. Microstructure of alloy exhibits a single-phase face-centred cubic (FCC) matrix embedded with the mixture of (Co, Cr, Fe)-rich tetragonal phase and Mo-rich rhombohedron-like phase. The morphologies of two intermetallics show matrix-based tetragonal phases bordered by Mo-rich rhombohedral precipitates around their perimeter. The experimental results presented in our paper provide key information on the microstructure and thermal stability of our alloy, which will assist in the development of similar thermal spray HEA coatings.