The application of amorphous alloy materials is limited by the behavior of small molding size and serious crystallization. With pure zirconium as the substrate, we herein adopted the selective laser melting technology to fabricate a 15 mm×15 mm×15 mm bulk Zr50Ti5Cu27Ni10Al8 amorphous alloy. The sample''s microstructure was analyzed. Moreover, the thermal effect of the preparation process of the bulk amorphous alloy was simulated using ANSYS finite element software. The research results show that the formed amorphous alloy sample is mainly composed of amorphous phase. Crystallization occurs in the superposition area of the heat affected zone because of the accumulation of structural relaxation and crystal embryos. The crystalline phase is Al5Ni3Zr2. This study provides a possibly effective method for preparing bulk amorphous alloy by laser additive manufacturing.