Two novel organic compounds incorporating 8-hydroxyquinoline moiety, namely 2-[2-(2,3-dichlorophenyl)vinyl]quinoline-8-ol (HL 1 ) and 2-[2-(3,5-dimethoxyphenyl)vinyl]quinoline-8-ol (HL 2 ), have been synthesized and their interaction with [ReO 2 (py) 4 ]Cl has been examined. The complexes [ReOCl(L 1 ) 2 ] (1) and [ReOCl(L 2 ) 2 ] (2) have been characterized spectroscopically and structurally. The experimental studies on the Re(V) complexes have been accompanied computationally by the density functional theory (DFT) and time-dependent DFT calculations. Additional information about binding between the rhenium atom and oxo ligand in the complexes 1 and 2 has been obtained by NBO analysis.