Icosahedral (I) particles with spherical morphology were found to appear as a primary precipitation phase in amorphous Zr 65 Al 7.5 Ni 10 Cu 12.5 M 5 (M=Ag, Pd, Au or Pt) alloys with two-stage crystallization process. The element M was selected with the aim of deviating the three empirical rules for stabilization of supercooled liquid, i.e., multicomponent of more than three elements, atomic size mismatch over 12%, and negative enthalpy of mixing. The I phase in an amorphous matrix has a small size of 25 to 40 nm. The second crystallization reaction results in the formation of Zr 2 Cu, Zr 2 Ni and Zr 2 Al 3 phases for the alloys containing Ag, Pd or Au, and Zr 2 Cu, Zr 2 Ni, Zr 2 Al 3 and ZrPt phases for the Pt-containing alloy. The Zr 65 Al 7.5 Ni 10 Cu 17.5 amorphous alloy crystallizes directly to a mixed structure of Zr 2 Ni, Zr 2 Cu, Zr 2 Al 3 and ZrNi phases through a single exothermic reaction. The addition of the element M is essential for the precipitation of the metastable I phase. The reason is that the structure changes from a long-range homogeneous configuration to an inhomogeneous one by the addition of the element M.