The influence of thermal treatment on structural changes in the Cu 47 Ti 33 Zr 11 Ni 8 Si 1 metallic glass has been monitored using X-ray diffraction (XRD) and differential scanning calorimetry (DSC). Additionally, the short-range order structure has been investigated by XRD using synchrotron radiation. The changes observed in the calorimetric behaviour cannot be quantified using conventional XRD. Small changes are, however, visible in the total structure factor S (Q) primarily in terms of amplitude of the oscillations, which tend to increase with increasing thermal treatment temperature. Real-space analysis of the pair distribution function suggests that the first coordination shell consists of three peaks, which can be modelled using Gaussian distributions. Furthermore, the synchrotron data also reveal changes in the local structure that occur during structural relaxation and early formation of nanocrystals at temperatures close to the experimentally determined crystallization temperature.