It has been reported that a quaternary Co 61.2 B 26.2 Si 7.8 Ta 4.8 alloy is a good glass former and can be laser-clad to an amorphous composite coating with superior hardness and wear resistance. In this paper, alloys with varying Ni contents to substitute for Co are coated on the surface of #45 carbon steel using a 5-kW CO 2 laser source for the purpose of obtaining protective coatings. In contrast to the quaternary case, the clad layers are characterized by a matrix of α-(Fe, Co, Ni) solid solution plus CoB, Co 3 B, and Co 3 Ta types of precipitates. The cladding layer is divided into four regions: Near-surface dendrites, α-(Fe, Co, Ni) solid solution plus dispersed particles in the middle zone, columnar bonding zone, and heat-affected area that consists of martensite. The hardness gradually decreases with increasing Ni content, and the maximum hardness occurs in the middle zone. Both the friction coefficient and wear volume are minimized in the alloy containing 12.2% Ni. Compared with the previous cobalt-based quaternary alloy Co 61.2 B 26.2 Si 7.8 Ta 4.8 , the addition of the Ni element reduces the glass-forming ability and henceforth the hardness and wear resistance of the clad layers.