The paper presents a combined experimental and computational study of tricarbonyl complexes fac-[Re(CO) 3 (L 1 /L 2 )Cl] (1a/1b) (L 1 =2-(methylthio)-N-((pyridine-2-yl)methylene)benzenamine and L 2 =2-(ethylthio)-N-((pyridine-2-yl)methylene)benzenamine). The Schiff base ligands L 1 and L 2 have been synthesized and characterized by elemental and spectroscopic analysis. Along with spectral characterizations, the structural confirmation by single crystal X-ray study has been done for complex 1a. The rhenium atom adopts a distorted octahedral geometry and is coordinated by three carbonyl ligands in a fac arrangement. The electronic structure, redox properties, absorption and emission properties of ligands and complexes have been explained based on DFT and TDDFT calculations. The complexes show MLCT bands at 443–448nm and emitted at 405–410nm upon excitation at 320–326nm, characterized as ILCT transitions.