Zr41.2Ti13.8Cu12.5Ni10.0Be22.5bulk metallic glasses were prepared by cooling the melt with a rate of about 10 K/s and investigated with respect to their chemical and structural homogeneity by atom probe field ion microscopy and transmission electron microscopy. The measurements on these slowly cooled samples reveal that the alloy exhibits phase separation in the undercooled liquid state. Significant composition fluctuations are found in the Be and Zr concentration but not in the Ti, Cu, and Ni concentration. The decomposed microstructure is compared with the microstructure obtained upon primary crystallization, suggesting that the nucleation during primary crystallization of this bulk glass former is triggered by the preceding diffusion controlled decomposition in the undercooled liquid state. ©1995 American Institute of Physics.