Divalent samarium incorporated in a barium octaborate matrix prepared by firing homogeneous precipitates has been studied with emission spectroscopy. One of the samarium sites associated with this product exhibits an extremely strong temperature dependence upon using an excitation wavelength of 532 nm. This effect allows for specific differentiation between the two major Sm(II) sites associated with this compound. Based on the assignment of the emission features to specific sites, the symmetry of the first samarium environment is thought to be C 3 or C 3v while that associated with the second site appears to be C 2v .