The metastable liquid phase separation and rapid solidification behaviours of Co61.8Cu38.2 alloy were investigated by using differential thermal analysis (DTA) in combination with glass fluxing, electromagnetic levitation (EML) and drop tube techniques. It is found that the liquid phase separation process and the solidification microstructures intensively depend on the experimental processing parameters, such as undercooling level, cooling rate, gravity level, liquid surface tension and the wetting state of crucible. Large undercooling and surface tension difference of the two liquids tend to facilitate further separation and cause severe macrosegregation. On the other hand, rapid cooling and low gravity effectively suppress the coalescence of the minority phase. Severe macrosegregation patterns are formed in the bulk samples processed by both DTA and EML. In contrast, disperse structures with fine spherical Cu-rich spheres homogeneously distributed in the matrix of Co-rich phase have been obtained in drop tube.