Fe-based amorphous alloys have exceptional properties such as low coercivity and core loss. In recent years, the development of amorphous alloys by using selective laser melting (SLM) technology has become the focus of attention. However, the glass-forming ability (GFA) and mechanical properties pose challenges for fabricating Fe-based amorphous alloys with complex geometries. This work aims to establish fundamental processing-(micro) structure-property links in Fe-based amorphous alloys processed by selective laser melting (SLM). With that purpose, a low-energy-input melt pool is achieved and the overlap quality between adjacent melt tracks and successive deposition layers is enhanced, through optimization of printing parameters. The Fe-based amorphous alloy is obtained with a high relative density of 94.3% and low coercivity of 0.5 Oe. Furthermore, the saturation magnetization of the printed alloy increases to 0.89 T compared with that of the powder feedstock. This work overcomes the mutual constraint between the GFA and part quality in fabricating of complex-structure Fe-based amorphous alloys, and is of great significance for promoting the application of Fe-based amorphous alloys.