In this study, TaMoCrTiAl refractory high-entropy alloy coating without defects was successfully prepared on the Ti6Al4V substrate by laser metal deposited. Microstructure and properties were investigated systematically by multiple characterization methods. The results of phase and morphology experiments indicate that the coating comprised a BCC phase and a partial Laves phase. The coating, with an average thickness of 990 μm, exhibits good metallurgical bonding with the substrate. Further observation reveals that the cladding region consists of irregular bulk crystals. The heat-affected zone has a fine grain size, whereas the substrate has coarse and uneven grains. The high-temperature oxidation test shows that the formation of an Al2O3 oxide layer enhances the coating's high-temperature oxidation resistance. According to the results of microhardness tests, the average microhardness in the coating is about 570.98 HV (1.87 times that of the substrate) due to the formation of the leave phase particles and the fine-grain strengthening. The presence of Titanium, chromium and molybdenum elements in the coating facilitates the formation of a passivation film, thereby enhancing its corrosion resistance. Furthermore, the coating exhibits the smallest grinding force (43.637 N) and the lowest roughness (0.506 μm) at an experimental temperature of 100 °C, which demonstrates that appropriately elevating the experimental temperature can decrease the grinding force and enhance the flatness of the grinding surface.