Phase formation in the Cu 47Ti 33Zr 11Ni 8Si 1 alloy synthesized by various solidification techniques has been studied using X-ray diffraction (XRD), differential scanning calorimetry (DSC) and transmission electron microscopy (TEM) paying, in particular, attention to the TEM sample preparation. While a reduced cooling rate results in a duplex microstructure, consisting of nanocrystals in an amorphous matrix, glass formation is achieved upon employing a faster quenching rate. The difference in composition and quench temperature influence the phase transition upon heating. The essential differences observed in TEM, notwithstanding the ion-milling effects and the different pre-alloy ingots used for metallic glass synthesis, can be linked to differences in the nucleation and growth mechanism which, in turn, is influenced by the chemical short range order (CSRO) obtained upon quenching.