Al–Cu–Ce alloys have been studied in the Al-rich corner using the microstructural (LM and SEM), thermal (direct and DSC), X-ray diffraction and electron probe microanalysis techniques. Three cross-sections were of particular interest: (a) at 20%Cu (up to 12.5%Ce), (b) at 14%Cu (up to 10%Cu) and (c) at a ratio Cu:Ce=2:1 (up to 10%Ce and 20%Cu). As-cast alloys and those after annealing at 540 and 590°C were studied. Boundaries of appearance of the Al8CeCu4 primary crystals and ternary eutectic involving the phase Al2Cu were determined. The radial cross section (Cu:Ce=2:1) is supposed to be of quasibinary type as ternary eutectic does not form. The temperature and concentrations of the eutectic reaction L–(Al)+CeCu4Al8 were found to be 610°C, 14%Cu and 7%Ce. This binary eutectic has fine microstructure and is capable to fragmentation and spheroidization during heating. The paper considers possibility of using the Al–Cu–Ce system for developing novel Al casting alloys with significantly improved casting properties (hot tearing and fluidity) in comparison with 2xx commercial alloys.