The main objective of this paper is the characterization of the spectroscopic properties of new materials that are prospective laser media. This approach allows for the comparison of the properties of the Cr3+ in different environments. Here, we have studied the photoluminescence and optical absorption of Cs2NaScF6:Cr3+ single crystals. On the basis of near-infrared luminescence measurements at 2, 77, and 300 K the observed lines originated from the Cr3+-centres were associated with the 4T2(4F) → 4A2(4F) transition and the lifetimes were obtained. In spite of the quenching observed as a function of temperature at least 10% of the 2 K emission intensity for Cs2NaScF6 doped with 1% of Cr3+ remains at room temperature. Besides, the 2 K emission broad band could be well described in terms of normal modes of the octahedral complex [CrF6]3-, and the Racah and crystal-field parameters calculated.