Several [Ru(bpy)(3)](2+) (bpy = 2,2'-bipyridine and its derivatives) complexes were synthesized and compared electrochemically and spectroscopically in the search for better luminophores for electrochemiluminescence (ECL)-based analytical applications. ECL measurement in [Ru(bpy)(3)](2+)/tripropylamine (TPA) aqueous buffer solutions has led to a conclusion that due to the complexity of the ECL generation process, the photoluminescence efficiency cannot be used to predict ECL intensity and there is no obvious relationship between the photoluminescence quantum yield and the ECL intensity. Under the present experimental condition, when compared with the pristine (Ru(bpy)(3))(2+), the ethoxycarbonyl-substituted derivative, [Ru(bpy-COOEt)(3)](2+) one of the most efficient luminophores under photoexcitation, did not generate reasonably intense ECL, whereas luminophores with lower photoluminescence quantum yields demonstrated higher ECL. These findings are useful for further efforts in the search for more efficient ECL luminophores.