The Zr55Cu30Ni5Al10 samples were prepared by 3D printing laser, and their microstructure and mechanical properties were studied. The results show that the relaxation enthalpy and crystallization enthalpy of the supercooled liquid region are greatly affected by the holding time, holding effect and temperature change of the sample. In the process of heat treatment, the higher the sample temperature is, the longer the holding time is. Because of the change of nanocrystals, the value of crystallization enthalpy is lower, and the relaxation enthalpy increases first and then decreases. In the supercooled liquid region, the heat treatment can increase the free volume of the HAZ and the molten pool in the 3D printing laser formed Zr based amorphous, and the hardness and modulus of the samples such as the HAZ and the molten pool will decrease in varying degrees. After heat treatment, the compressibility of 3D printing laser formed Zr based amorphous decreases significantly.