Several BrRe(CO)3L complexes (where L groups are 2,2’-biquinoline substituted in the 3 and 3’ positions) were prepared. Their pseudooctahedral fac structure was established by using FTIR, UV-vis, and H-1-NMR and confirmed by X-ray analysis. A good correlation between the electrochemical parameters and the MLCT electronic transition was found. The crystalline compound, BrRe(CO)3(3,3’-trimethylene-2,2’-biquinoline) belongs to triclinic space group P1BAR with a = 9.113(11) angstrom, b = 10.192(4) angstrom, c = 12.825(5) angstrom, alpha = 73.23(4)degrees, beta = 81.30(7)degrees, and gamma = 66.55(5)degrees. The volume of the unit cell is 1048(1) angstrom3 with Z = 2. The structure was refined to R = 0.040.