A series of samarium β-diketonates comprising nitrogen-heterocyclic auxiliary moiety were synthesized and characterized spectroscopically. A comprehensive analysis of complexes suggests the octacoordinated environment about samarium ion and similar structural behavior of complexes. The samarium ion is coordinated via carbonyl oxygen of diketone unit and nitrogen of neutral ligand. Energy band gap values of complexes lie in range of semiconducting materials. The photophysical properties of complexes were evaluated from photoluminescence spectra of complexes. By examining the energy transfer pathway and emission spectra, the sensitizing nature of chromophoric ligands is revealed. These synthesized complexes have shown peak around 649 nm (4G5/2→6H9/2) due to electric dipole transition. Results of luminescence spectra and colorimetric analysis have demonstrated the emission of synthesized samarium complexes in reddish orange region. The optical and photophysical properties of complexes claim the usefulness of prepared samarium complexes in designing display devices.