The glass-forming ability (GFA) of alloys with a high-solvent content such as soft magnetic Fe-based and Al-based alloys is usually limited due to strong formation of the solvent-based solid solution phase. Herein, we report that the GFA of soft magnetic Fe-based alloys (with >70 at.% Fe to ensure large saturation magnetization) could be dramatically improved by doping with only 0.3 at.% Cu which has a positive enthalpy of mixing with Fe. It was found that an appropriate Cu addition could enhance the liquid phase stability and crystallization resistance by destabilizing the α-Fe nano-clusters due to the necessity to redistribute the Cu atoms. However, excessive Cu doping would stimulate nucleation of the α-Fe nano-clusters due to the repulsive nature between the Fe and Cu atoms, thus deteriorating the GFA. Our findings provide new insights into understanding of glass formation in general.