The luminescence properties of Tm2+-doped BaCl2 with an orthorhombic structure have been studied as a function of temperature and compared to other Tm2+-doped chlorides. In addition to the 2F5/2 → 2F7/2 (4f13 → 4f13) line emission, two 4f125d1 → 4f13 band emissions are observed at 20 K that can be ascribed to the spin-allowed (3H6,5d1)S=1/2 → 2F7/2 and spin-forbidden (3H6,5d1)S=3/2 → 2F7/2 transitions. So far, the Tm2+ spin-allowed (3H6,5d1)S=1/2 → 2F7/2 transition has only been identified in Tm2+-doped iodides and some bromides but never before in a Tm2+-doped chloride. Its presence in orthorhombic BaCl2:Tm2+ is explained by the absence of a (3H6,5d1)S=1/2 → (3H6,5d1)S=3/2 energy transfer process. As the temperature increases, both 4f125d1 → 4f13 emissions undergo rapid quenching and are no longer observed at 120 K, resulting in an intensity increase of the 4f13 → 4f13 emission. However, above 100 K, the intensity of the 4f13 → 4f13 emission also decreases, most likely due to quenching via (3H6,5d1)S=3/2 → 2F7/2 interband crossing, as enabled by the exceptionally large 4f125d1 Stokes shift.