In this paper, the electronic structure and the luminescence properties of Mn (1 mole%)-doped SrS phosphors synthesized by using the solid state diffusion method are reported. The X-ray diffraction pattern reveals a single-phase rocksalt structure, and the average crystallite size calculated using a Williamson-Hall plot is 72 nm. The near-edge X-ray absorption fine structure (NEXAFS) collected at Mn L3,2-edges confirms the presence of divalent Mn in SrS. A bright green photoluminescence (PL) at 547 nm is observed at an excitation wavelength of 355 nm, which may be attributed to the 4T1-6A1 inner atomic transition of the 3d electrons in the Mn2+ ion under the cubic crystal field of SrS. We have also studied the thermoluminescence (TL) of UV (254 nm)-irradiated Mn-doped SrS phosphors. The TL glow curve has a well-resolved single peak around 360 K, which shifts slightly to lower temperatures with increasing UV exposure time, confirming second-order kinetics. A kinetic analysis of the experimental TL glow curve has been carried out using Chen’s peak shape method to determine the trapping parameters.