The thermodynamic parameters of all stable phases in the Ni-Zr system are reported in this paper. The available experimental data are taken into account in deriving the interaction parameters of various phases. The Ni7Zr2, Ni21Zr8, Ni11Zr9, NiZr, and NiZr2 phases are treated as stoichiometric. The solid solubility of the Ni5Zr, Ni3Zr, and Ni10Zr7 phases are described using a two sublattice model. The calculated thermodynamic properties and the phase diagram are in good agreement with the experimental ones. The thermodynamic parameters, along with the classical nucleation and crystal growth theory, have been used to explain the formation of metastable noncrystalline and crystalline phases upon rapid quenching of the liquid alloys. It has been demonstrated that even without any prior knowledge of the physical property, such as glass transition or crystallization temperature and thermodynamic property, such as the enthalpy of amorphous → crystal transformation of the amorphous alloy, it is possible to make a reasonably good “first order prediction” of the glass-forming range in a binary system. The experimentally determined glass-forming range in the Ni-Zr system is found to be in good agreement with the predicted one.