The luminescence properties of Sm<sup>2+</sup>-activated stoichiometric and non-stoichiometric Ba<sub>2</sub>B<sub>5</sub>O<sub>9</sub>Cl were investigated from 16 to 450 K. In stoichiometric Ba<sub>2</sub>B<sub>5</sub>O<sub>9</sub>Cl, the emission spectra of Sm<sup>2+</sup> are composed of 4f<sup>6</sup>→4f<sup>6</sup> transitions over the 16–450K temperature range studied. Luminescence was observed from Sm<sup>2+</sup> in four inequivalent cationic sites at 16K and two inequivalent sites at room temperature. In the non-stoichiometric compound, the emission is characterized by 4f<sup>6</sup>→4f<sup>6</sup> transitions at low temperature and 4f<sup>5</sup>5d<sup>1</sup>-4f<sup>6</sup> transitions at high temperature. The Sm<sup>2+</sup> doped into the Ca<sup>2+</sup> and Sr<sup>2+</sup> analogues in the M<sub>2</sub>B<sub>5</sub>O<sub>9</sub>Clseries shows the broadband 4f<sup>5</sup>5d<sup>1</sup>-4f<sup>6</sup> luminescence in both the stoichiometric and non-stoichiometric compounds due to the increased ligand field caused by the smaller ionic radii of the metal ions.