A series of o-phenanthroline-substituted ruthenium(II) complexes containing 2,2'-dipyridyl, 2-(2-pyridyl)benzimidazole, 2-(2-pyridyl)-N-methylbenzimidazole, 4-carboxymethyl-4'-methyl-2,2'-dipyridyl, and/or 4,4'-dimethyl-2,2'-dipyridyl ligands were synthesized and examined as potent electrochemiluminescent (ECL) materials. The characteristics of these complexes, regarding their electrochemical redox potentials and relative ECL intensities for tripropylamine were studied. As found in a 2,2'-bipyridyl-substituted ruthenium(II) complexes, a good correlation between the observed ECL intensity and the donor ability of alpha-diimine ligands was observed, i.e., the ECL intensity of the Ru(II) complex decreased with an increase in the ligand donor ability. The ECL efficiency increased as the number of substitutions of o-phenanthroline (o-phen) to metal complexes increased.