The cubic Laves-phase aluminides REAl2 with RE = Sc, Y, La, Yb and Lu were prepared from the elements by arc-melting or using refractory metal ampoules and induction heating. They all crystallize in the cubic crystal system with space group Fd3̄m and adopt the MgCu2 type structure. The title compounds were characterized by powder X-ray diffraction and spectroscopically investigated using Raman and 27Al and in the case of ScAl2 by 45Sc solid-state MAS NMR. In both, the Raman and NMR spectra, the aluminides exhibit only one signal due to the crystal structure. DFT calculations were used to calculate Bader charges illustrating the charge transfer in these compounds along with NMR parameters and densities of states. Finally, the bonding situation was assessed by means of ELF calculations rendering these compounds aluminides with positively charged REδ+ cations embedded in an [Al2]δ- polyanion.