In this work, we report the first spectroscopie observation of octahedrally coordinated pentavalent chromium ions in BaCaMg aluminate glasses. A broad band emission peaking at 780 nm with band width of 3000 cm−1 has been observed at 12K. The measurements of fluorescence decay, time-resolved emission and excitation spectra reveal that the emission band is an overlapped luminescence originating from both the 2E to 2T2 transition of octahedrally coordinated Cr5+ and a charge transfer transition of Cr6+O4 groups.