We present here the electronic structure and photoluminescence properties of Sm (0.1-1.0 mol%) doped SrS phosphors. The doping in SrS was probed by near-edge X-ray absorption fine structure (NEXAFS) at M-5,M-4-edges of Sm in total electron yield mode. The simulated absorption edges using atomic multiplet calculations were correlated with experimental results, which clearly reveal the presence of trivalent state of Sm in SrS matrix. However, for Sm (1 mol%), very minor traces of Sm2+ were also observed, which have been explained by comparing the NEXAFS spectra in total electron and florescence yield mode. The PL emission of SrS: Sm comprises of three sharp bands at 567, 602 and 650 nm owing to the well-known intra 4f transitions from (4)G(5/2) to H-6(J) (J = 5/2, 7/2, 9/2) levels of Sm3+ ions in SrS host. The effect of Ce co-doping on SrS:Sm phosphors was also investigated, which exhibits characteristic PL emission of independent ions at their respective excitation wavelengths. However, at an excitation wavelength of 393 nm, SrS: Ce, Sm exhibits the simultaneous characteristic PL emission of both ions spanning into blue-green-red region. The CIE chromaticity coordinates also clearly show the influence of excitation wavelengths on the emission colour of SrS: Ce, Sm. (C) 2012 Elsevier B. V. All rights reserved.