Single layer and multilayer Zr55Al10Ni5Cu30 bulk metallic glasses are deposited on the commercial pure zirconium substrates by laser solid forming (LSF). The composition and microstructure of the deposits are researched. The results show that the deposits are mainly constituted by amorphous materials. The crystallization degree does not increase remarkably with the increase of deposited layers. The crystallization mainly occurs in the overlapping zone between the adjacent traces and layers of the heat affected zone (HAZ), especially the adjacent layers. The bonding type between deposit and substrate is metallurgy bonding. There is epitaxial growth of dendrites emerging at the thin transition zone which is only 35 μm, the composition dilution mainly occurs in this transition zone.