Terpyridine ligands are widely used in chemistry and material sciences owing to their ability to form stable molecular complexes with a large variety of metal ions. In that context, variations of the substituents on the terpyridine ligand allow modulation of the material properties. Applying the Stine cross-coupling reaction, we prepared with good yields a new series of terpyridine ligands possessing quinoline-type moieties in ortho, meta, and para positions and dimethylamino substituents at central or distal positions. The corresponding cobalt(II) complexes were synthesized and fully characterized by elemental analysis, single-crystal X-ray crystallography, mass spectrometry, and UV-vis, H-1 NMR, and Fourier transform infrared (FT-IR) spectroscopy as well as by cyclic voltammetry (CV). Density functional theory (DFT) calculations were performed to investigate the electronic structure of all the Co(II) bis-terpyridyl molecular complexes. In this work, we show that terpyridine ligand functionalization allows tuning the redox potentials of the Co(III)/Co(II), Co(II)/Co(I), and Co(I)/Co(I) (tpy)(center dot-) couples over a 1 V range.