High-entropy alloys are used as surface-modified cladding materials for parts due to their high comprehensive properties. In this paper, a FeCoCrNiAlMox (x = 0, 0.75, 1.0, molar ratio) coating was prepared on the surface of 2Cr13 substrate by laser cladding method, and the mixing entropy of the actual composition of the coating was calculated. The microstructures of different coatings were compared and analyzed by OM and SEM. The composition of different micro-domains of the coatings was analyzed by EDS of scanning electron microscope, and the effect of Mo was explored. The results show that Mo0, Mo0.75, and Mo1.0 are high-entropy alloy coatings, and obvious delamination occurs in the coatings. The microstructures from the bonding area to the cladding area are plane crystal, columnar dendrite, and columnar crystal. With the addition of molybdenum element, the dendrites decrease, the columnar crystals increase, and the structure become finer. The atomic percentage of Mo element in the pre-crystallization area is larger than that in the post-crystallization area; while for Al element, on the contrary; Fe element in the matrix is diluted to the cladding layer, and the needle-like and granular precipitates at the top of the cladding layer that are rich in Cr and poor in Al are preliminarily judged to be α-Cr phase. This study provides an information basis for the microstructure, composition analysis, and application of FeCoCrNiAlMox high-entropy alloy coatings.