Non-equilibrium solidified Cu100-xZrx(x=5, 30, 50) alloys with different compositions were prepared by vacuum induction melting and spray casting method. The microstructure evolution including grain morphology, element distribution and phase components of non-equilibrium solidified alloy was presented by optical microscope, scanning electron microscope, energy spectrum analysis and X ray diffraction technique. The solidification process of the alloys was studied by differential scanning calorimetry. The results show that the volume fraction of primary phase increases continuously with the increase of Zr content and reveals a transition from non-faceted to faceted and finally non-faceted phase. Affected by the fast cooling effect of copper mould, both the peritectic transformation in Cu70Zr30 alloy and eutectoid transformation in Cu50Zr50 alloy are suppressed, which are further verified by the thermal analysis curve under slow cooling condition. Consequently, the formation regularity of non-equilibrium microstructure of spray casted Cu-Zr alloy can be well explained.