Strontium hexaborate doped with samarium (SrB6O10: Sm) was synthesised using a high-temperature solid-state reaction. X-ray powder diffraction confirmed the phase formation of the SrB6O10 materials, and the scanning electron microscopy images showed plate-like morphology of the samples. The photoluminescence results showed that the material could be excited by 240–560 nm radiation, and emission between 540 and 680 nm relating to 4G5/2→6HJ (J = 5/2, 7/2, and 9/2) transitions of the trivalent samarium (Sm3+) ion, and between 680 and 830 nm relating to 5D0→7FJ (J = 0, 1, 2, 3, and 4) transitions from the divalent samarium (Sm2+) ion could be observed. To enhance the emission from the Sm2+ ions, the material was co-doped with Mg, Ca, Ba, Y, La or Eu. SrB6O10: Sm, Mg showed the most intense Sm2+ emission compared to the other samples. Co-doping with Mg enhanced the Sm2+ emission intensity by a factor of 9.9.