Stellite 6 cobalt-based alloy powder was used to produce Co–Cr–W alloy using laser additive manufacturing technology, and then different heat treatment strategies were carried out on the deposited sample. The characteristics of microstructure under different heat treatment conditions were investigated using scanning electron microscopy with energy dispersive spectroscopy, transmission electron microscope, and x-ray diffraction. The results show that the as-deposited sample has few cracks or pores, and the microstructure is typical dendritic structure, and lamellar eutectic carbides are rich in Cr in interdendritic. The matrix mainly consists of γ phases and a few ϵ phases. Some γ phases transform into ϵ phases after 900°C/6 h aging treatment and lamellar eutectic carbides transform into blocky carbides presenting as a network, most of the carbides are rich in Cr and a few are rich in W. When heat treated at 1200°C/1 h followed by water cooling and then treated at 900°C/6 h followed by furnace cooling, it can be found that some γ phases transform into ϵ phases. The carbides transform into elliptical M23C6 carbides that are rich in Cr with the size of 1 to 3 μm and a part of W-rich carbides.