A series of ruthenium(II) complexes of polypicolylamine ligands have been prepared. The reaction of Ru(PhCN) 4 Cl 2 with the tridentate ligand N,N-bis(2-pyridylmethyl)aniline (phdpa) followed by precipitation with PF 6 - salts affords the complex, [Ru(phdpa) 2 ](PF 6 ) 2 . The crystal structure of [Ru(phdpa) 2 ](PF 6 ) 2 shows that the ligand coordinates in a facial mode, with sp 3 -nitrogens located cis to each other. The reaction of Ru(dmso) 4 Cl 2 with the tetradentate ligand tris(2-pyridylmethyl)amine (tpa) in ethanol yielded the (Cl, N a m i n e )-trans [Ru(tpa)(dmso)Cl](PF 6 ) complex which was characterized by X-ray crystallography. [Ru(tpa)(dmso)Cl](PF 6 ) reacts with bipyridine, tpa and tricyanomethane anion (tcm) affording the [Ru(tpa)(bipy)](PF 6 ) 2 , [Ru(tpa) 2 ](PF 6 ) 2 and Ru(tpa)(tcm) 2 complexes, respectively. The structures of [Ru(tpa)(bipy)](PF 6 ) 2 and Ru(tpa)(tcm) 2 show that tpa acts as a tetradentate ligand, while in [Ru(tpa) 2 ](PF 6 ) 2 it is tridentate, facially coordinated, with one non-coordinated pyridine.