The terdentate ligand 2,2′:6′,2′′-terpyridine (tpy) has increasingly become one of the most popular ligands in coordination chemistry. A variety of substituents are utilised to tailor the properties of its metal complexes. 2,2′:6′,2′′-Terpyridine was reacted with almost all transition metals to form complexes. Among a series of tpy ligand derivatives, those containing substituents at the C(4′) position are of especial interest. Metal-bonded tpy ligands with spacers at C(4′) provide a means of directionality, and thus a means of linear communication, it means that electronic communication can occur along the coordination axis. In addition, the insertion of a single substituent at the C(4′)-position of the tpy ligand results in no enantiomeric derivatives, as the derivative retains its plane of symmetry. The synthetic strategies used to prepare tpy ligands are reviewed comprehensively.