Early, the efficiency of the CALPHAD (Calculation of Phase Diagrams) method to a targeted search for compositions of amorphous alloys has been shown. The method for predicting the ranges of amorphization is based on the calculation of diagrams of metastable phase transformations between supercooled melts and boundary solid solutions on the base of pure elements. In this work, the model parameters for thermodynamic properties of liquid alloys and boundary solid solutions were summarized in a self-consistent database for the multicomponent Cu–Fe–Ni–Ti–Zr–Hf system. Such database for the multicomponent system is based on a common set of model parameters for boundary binary and ternary systems. This database was used to predict the concentration ranges of amorphization for the quinary Cu–Fe–Ni–Ti–Zr, Cu–Fe–Ni–Ti–Hf and boundary ternary and quaternary systems. The results of calculations are presented along sections in quaternary and quinary systems. The ternary and quaternary equiatomic alloys along with high entropy CuFeNiTiZr and CuFeNiTiHf alloys are trapped into prognosed composition ranges of amorphization. Predicted composition space of amorphization for melts of the Fe–Ni–Ti–Zr system is shown on the concentration tetrahedron. Based on the obtained results, a new criterion for predicting the concentration regions of amorphization of multicomponent melts is proposed, according to which the presence of a sufficient content of metals that are electron acceptors and donors is a chemical factor that affects the thermodynamic stability of melts and determines their glass-forming ability. For multicomponent melts of the Cu–Fe–Ni–Ti–Zr–Hf system the concentration ranges of amorphization correspond to the simultaneous fulfillment of the conditions xFe + xNi + xCu > 0.25 and xTi + xZr + xHf > 0.15, where Fe, Ni, and Cu are electron acceptors and Ti, Zr, and Hf are electron donors.
