Interest in 3d transition metal impurities in ionic crystals has increased due to their important role in the laser activity of these materials. Moreover, recent advances in tunable solid-state lasers and high-power semiconductor laser diode arrays have generated a strong interest in investigating new compounds that emit in the visible and near-infrared spectral regions. In particular, many optical studies have been devoted to Cr³⁺-doped fluoride crystals as a consequence of the high quality of some Cr³⁺-based laser materials. In the present investigation, the low-temperature emission spectra of Cr³⁺ ions in the hexagonal elpasolites Cs₂NaAlF₆ and Cs₂NaGaF₆ have been measured. Each compound has two crystallographically inequivalent octahedral sites for the Al³⁺ and Ga³⁺ ions that can be occupied by Cr³⁺ ions. For both materials, the luminescence spectrum presents two zero-phonon lines accompanied by a well-defined vibrational structure. The different peaks of the emission broad band are described in terms of phonons of the lattice and normal modes of the octahedral complex [CrF₆]^3-. A detailed analysis of the vibrational structure observed leads to the conclusion that the ²E and ⁴T₂ excited states of the [CrF₆]^3- ion are displaced along the e_g and a_1g and probably the t_2g coordinates.