Ru(bpy)3Cl2 was used to modify the glass carbon electrodes (GCE) by oxidation and co-deposition on the electrode surface. The modified electrodes were characterized by atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). About 2.2 × 10−9 mol Ru(bpy)32+ was immobilized on the GCE surface (ϕ = 4 mm). The modified GC electrodes showed stable electrochemiluminescence with tripropylamine (TPrA) as the co-reactant with a linear range from 10 to 500 μM (R2 = 0.999). Among the 10 amino acids tested, the modified electrode system showed selective response to arginine and lysine, indicating that the molecular structure played an important role as co-reactant. This simple and sensitive electrode modifying method when combined with flow-injection or liquid chromatography systems has the potential for amino acid analyses.