The 457.9 nm and 514.5 nm laser excited spectra of polycrystalline Cs 2NaEuCl 6 at room temperature and 120 K are reported. The spectra are interpreted in terms of: (a) Raman transitions involving fundamental modes of the EuCI 6 3− moiety, with some features exhibiting different relative intensity as a function of excitation line; (b) Raman transitions involving lattice modes and combination bands with the phase transition soft mode; (c) electronic Raman bands of Eu 3+; and (d) luminescence bands from the electronic and/or vibronic levels of ( 5 D 2)Γ 3,Γ 5, ( 5 D 1)Γ 4 and ( 5D 0) Γ 1 to the electronic and/or vibronic levels of 7 F J (J=0−6) . The 120 K and 10 K infrared absorption spectra of Cs 2NaEuCl 6 are reported, and assigned in detail to the transitions involving terminal crystal field and/or vibronic levels of 7F J ( J=2–6). A complete interpretation is given for the vibronic structure of the transitions. Together with the electronic Raman and luminescence results, all of the energy levels of Eu 3+ in Cs 2NaEuCl 6 up to 21 500 cm −1 have been assigned. At 120 K, the effects of the phase transition are not apparent from the moiety modes of Cs 2NaEuCl 6, but the caesium translational mode in the Raman spectrum is split. The degenerate electronic levels exhibit splittings of up to several wavenumbers. A comparison is made with the corresponding spectra of Cs 2LiEuCl 6, and a vibrational analysis is given for both compounds. The principal stretching force constant is about 10% greater in Cs 2NaEuCl 6 than in Cs 2LiEuCl 6, whereas the principal bending force constant is about 30% smaller.