The effect of cooling rate on the microstructure of Cu80Cr20 alloys was studied by using vacuum non-consumable arc melting, vacuum induction melting, electromagnetic levitation and splat quenching. The microstructure evolution of the Cr-rich were analyzed by scanning electron microscopy (SEM) and optical microscopy. The results showed that nonuniform Cr-rich dendrite distributes on Cu-rich matrix for arc melted alloys and uniform Cr-rich dendrite distributes on Cu-rich matrix for electromagnetic levitation melted alloys and vacuum induction melted alloys. However, the Cr-rich phase show both dendrites and spheroids for splat quenched alloys. This means liquid phase separation occurred during rapid solidification.