TiVCrAlSi high entropy alloy coatings were deposited on Ti–6Al–4V alloy by laser cladding. SEM, XRD and EDS analyses show that, the as-clad coating is composed of (Ti,V) 5 Si 3 and a BCC solid solution. After annealing at 800°C for 24h under vacuum, the coating is composed of (Ti,V) 5 Si 3 , Al 8 (V,Cr) 5 , and a BCC solid solution. The temperature-dependent phase equilibrium for the coating material calculated by using the CALPHAD method, indicates that above 880°C the stable phases existing in the coating material are a BCC solid-solution and (Ti,V) 5 Si 3 . When the temperature is below 880°C, the stable phases are (Ti,V) 5 Si 3 , Al 8 (V,Cr) 5 , and a BCC solid solution. In order to validate the calculation results, they were compared with TiVCrAlSi alloy samples prepared by arc melting, encapsulated in quartz tubes under vacuum, annealed at 400–1100°C for 3days and water-quenched. XRD analysis shows that the experimental phase composition agrees with the thermodynamic calculations. After vacuum annealing, there is a small increase of hardness for the laser clad TiVCrAlSi coating, which is due to the formation of Al 8 (V,Cr) 5 . The oxidation tests show that the TiVCrAlSi coating effectively improves the oxidation resistance of Ti–6Al–4V at 800°C in air. The formation of a dense and adherent scale consisting of SiO 2 , Cr 2 O 3 , TiO 2 , Al 2 O 3 and a small amount of V 2 O 5 is supposed to be responsible for the observed improvement of the oxidation resistance.