Cu-Hf-Al alloys are considered to be relatively new ones among Cu-based bulk amorphous alloys. Cu-Hf-Al alloys have high strength in amorphous state and this property makes many applications feasible for the industry. During the production of amorphous alloys the most important purpose is to produce them in the biggest diameter to make them suitable for a wide range of applications. The circumstances of the production process have a great influence on the developing structure. In the present work solidification of Cu-Hf-Al alloys were investigated. The alloys were cast into different shapes with different Al contents with special regard to the appearance of the amorphous/crystalline structure. The appearance and the structure of crystalline phases were determined by X-ray diffraction and X-ray, DSC and metallographic measurements were used to investigate the developing structure.