In the present work, the glass forming ability (GFA) and its compositional dependence on Al–Ni–Ce system alloys were investigated as a function of several thermal parameters. Rapidly quenched Al 85 Ni 15− X Ce X (X=4,5,6,7,10), Al 90 Ni 5 Ce 5 , Al 89 Ni 2.4 Ce 8.6 , Al 80 Ni 15.6 Ce 4.4 and Al 78 Ni 18.5 Ce 3.5 amorphous ribbons were produced by melt-spinning and the structural transformation during heating was studied using a combination of X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The results showed that the GFA and the thermal stability in the Al-rich corner of Al–Ni–Ce system alloys were enhanced by increasing the solute content and specifically the Ce content.