In the present study, the extensive efforts had been made to attain the higher-quality Zr-Cu based ribbons by optimizing the fabrication process. Under the same preparation conditions, the as-spun Zr-Cu based ribbons with the different amorphous state can be obtained by tailoring the chemical compositions. The microstructure of the as-spun Zr50Cu50 ribbon was featured with the amorphous matrix embedded with the B2 crystalline and the superior mechanical properties can be achieved as a result of the martensitic transformation induced by stress during deformation. The partial substitute of Cu by Ni and Co enhanced the ability of forming the amorphous Zr-Cu-Ni-Co ribbons and the size of the B2 crystalline gradually became smaller. The reduction of B2 crystalline in the amorphous matrix led to the slight decrease in the mechanical properties of the as-spun Zr-Cu based ribbons. However, the microstructure of the annealed Zr-Cu based ribbons was characterized by the nanoscale grain. Meanwhile, the nano-scale Cu10Zr7 precipitates distributed in the nanograin. The grain refinement and precipitation strengthening contributed to the superior mechanical properties of the annealed Zr-Cu based ribbons.