The structure change of Cu55Zr45 metallic glass during natural and artificial ageing was investigated with EXAFS method. For comparison, the structure of quenched specimen was also determined. The corresponding phenomena after the specimen was aged artificially was studied with the small angle X-ray scattering and DSC, which are suitable for observing structure relaxation. Finally, according to the facts observed, a model of phase separation was suggested to explain the EXAFS of the specimens and their change during ageing.