Langebeinite (K2Ca2(SO4)3) ceramics doped with increasing concentrations of Nd3+ ions (0.01–0.04 mol%) was prepared by wet chemical precipitation and calcination at 800 °C. Thermal studies revealed high temperature stability of the phosphors. UV–VIS-NIR spectroscopic analysis of phosphors reveal strong absorption peaks representing f → f transitions. Direct bandgap derived from Kubelka-Munk plot was found to be ~5.66 eV. FTIR studies reveal tetrahedral symmetry of the SO42− ions. SEM micrographs reveal the formation of phosphors with wide particle size distribution and elemental composition was analysed using EDX studies. Scintillation studies representing a single high intensity peak around 784 nm is ascribed to 4I9/2 → 4F5/2 + 2H9/2 transition. Langbeinite phosphor with 0.02 mol% of Nd3+ exhibited maximum emission intensity indicating optimal concentration for scintillation studies favouring the development of NIR emitting phosphors.