In view of possible applications it is compelling to design alloys with new compositions of a high glass forming ability (GFA). This parameter is crucial for bulk metallic glasses (BMGs), which gain increasing interest due to the outstanding combination of properties, e.g. ductility, wear or corrosion resistance. A method based on the semi-empirical Miedema's and geometric model confirms the significant GFA in ternary Y–Cu–Al system. Results of calculations are the basis for subsequent experimental works concerning synthesis and investigations of quasi-ternary Y(Ce)–Cu–Al glasses. Samples in the shape of ribbons were produced by a single-roller rapid quenching technique. Increasing the partial substitution of Y by Ce in four component Y x Ce 50−x Cu 42 Al 8 alloy, gives rise to a gradual change from nonmagnetic to magnetic behavior, which offers additional flexibility in its functionality and is of fundamental interest in the context of heavy-Fermion behavior and composition-driven quantum phase-transitions in cerium intermetallic compounds. Heat capacity results for as-quenched Y x Ce 50−x Cu 42 Al 8 (0≤x≤50) amorphous alloys in the temperature range 2–200K are presented to discuss Y–Ce substitution effect. Deviation from Curie–Weiss law and anomaly in the temperature dependence of resistivity were observed and interpreted as the formation of 4f-derived electronic band state and proof of the weak localization of electrons.