During the crystallization study of the bulk metallic glass 46.8Ti8.2Cu7.5Ni10Be27.5 (Vit4) we have demonstrated that the primary crystals appearing during isothermal annealing in the glass region, above Tg and before Tx, were of quasicrystalline nature and beryllium free. The formula of the quasicrystalline phase so obtained and determined by electron techniques (EDX and EELS) was Zr63Ti14.4Ni12.4Cu10.2. We have synthesized phases in the system Zr75-xTixCu25-yNiy by melt spinning and obtained either amorphous or quasicrystalline phases. For the amorphous phases, we have studied the crystallization by in-situ neutron diffraction and obtained quasicrystals as primary crystals. Neutron and X-ray diffraction, DSC studies are presented.