A convenient synthesis of tris-heteroleptic polypyridyl [Ru(pp)(pp′)(pp″)]2+ complexes is reported (where pp,pp′, and pp″ represent three different polypyridyl ligands). Photolysis of [BzRu(pp)Cl]Cl (Bz = η6-C6H6) gives a mixture of Ru(pp)(CH3CN)2Cl2 and [Ru(pp)(CH3CN)3Cl]Cl. Refluxing this mixture with pp′ yields Ru(pp)(pp′)Cl2. Finally, refluxing Ru(pp)(pp′)Cl2 with pp″ in a 75% ethanol/water solution gives [Ru(pp)(pp′)(pp″)]2+. No ligand scrambling is observed. The complexes are characterized by 1H NMR, elemental analysis, FAB-MB, UV-vis and emission spectroscopy, and cyclic voltammetry.