Two hetero-tritopic bridging ligands L1 and L2 based on 2,2′-bipyridine and 1,10-phenanthroline moieties, and their corresponding Ru(II) complexes [{Ru(bpy)2}3(µ3−L1)](PF6)6 and [{Ru(bpy)2}3(µ3−L2)](PF6)6 (bpy = 2,2′-bipyridine), were synthesized. The molecular structures of both complexes were deduced by 1H NMR, ESI-MS, ESI-HRMS, elemental analyses, and IR spectroscopy. Quantum calculations on the free bridging ligands and their complexes are also presented. Both complexes display MLCT absorptions at around 454 nm, and emissions at around 613 nm in CH3CN solution at room temperature and at around 590 nm in EtOH–MeOH glassy matrix at 77 K. Cyclic and differential pulse voltammetry studies of both complexes reveal one reversible Ru(II)-centered oxidation and three reversible ligand-centered reductions, in each case.