The broad bands in the room-temperature excitation spectra of Sm 3+-, Dy 3+- and Tm 3+-activated Ca-α-SiAlON phosphors are interpreted as the N 3−-to-rare earth charge transfer transition (CTT). From the energies of the charge transfer transitions and from the optical data presented for the Eu 2+ ion, the location of the divalent rare earth ion energy levels relative to the valence and the conduction band of Ca-α-SiAlON is derived. The salient features of the energy-level diagram are shown to be practical in explaining the temperature-dependent variations of the Eu 2+ and Yb 2+ luminescence efficiency in Ca-α-SiAlON. A comparative study pertaining to the nature of the Yb 2+ and Eu 2+ ion luminescence in Ca-α-SiAlON and in SrSi 2O 2N 2 is presented. A tentative energy-level diagram of the trivalent rare earth ions in Ca-α-SiAlON is also constructed.