Cu47Ti33Zr11Ni8Si1 metallic glass powder was prepared by gas atomization. Decomposition in the amorphous alloy and primary crystallization has been studied by differential scanning calorimetry (DSC), x-ray diffraction (XRD), and transmission electron microscopy (TEM). The glassy powder exhibits a broad DSC exotherm prior to bulk crystallization. Controlled annealing experiments reveal that this exotherm corresponds to a combination of structural relaxation and nanocrystallization. A uniform featureless amorphous contrast is observed in the TEM prior to the detection of nanocrystals of 4–6 nm in size. High-resolution TEM studies indicate that this nanocrystalline phase has a close crystallographic relationship with the γ–CuTi phase having a tetragonal structure. The product of the main crystallization event is also nanocrystalline, hexagonal Cu51Zr14, having dimensions of 20 nm. However, there is no evidence for possible amorphous phase separation prior to the nanocrystallization events.