Due to their unique electronic and photophysical properties, rhenium(I) fac-tricarbonyl complexes of general formula [Re(N^N)(CO)₃X]ⁿ⁺ have been arousing constant interest in many diverse fields and applications, such as CO₂ (photo)electroreduction, organic light emitting diodes and materials, sensors, biological applications and bio-imaging. The photophysical properties of [Re(N^N)(CO)₃X]ⁿ⁺ complexes can be modulated by structural variations of the ligands. Modifications of the N^N diimine ligand and of the axial X ligand have been deeply investigated. However, thiolate ligands have scarcely been used in the synthesis of rhenium tricarbonyl complexes. We describe the synthesis of a series of Pyta and Tapy-based Re(I) fac-tricarbonyl complexes with diversely para-substituted arenethiolates in the coordination sphere and report on the electrochemical, photophysical properties and DFT studies of such complexes.