Due to the highly sensitive electrochemiluminescence (ECL), tris(2,2′-bipyridyl) ruthenium(II) (Ru(bpy)32+) is often used in the field of bioarrays with the help of co-reactants. However, the generally used co-reactant, tripropylamine (TPA), is toxic, corrosive and volatile. Therefore, the search for safe, sensitive and economical co-reactants is critical. Herein, three aminocarboxylic acids, ethylenediamine-tetraacetic acid (EDTA), nitrilotriacetic acid (NTA), and 2-hydroxyethylethylene diaminetriacetic acid (HEDTA), have been investigated as potential co-reactants for promoting Ru(bpy)32+ ECL behaviour. A possible ECL mechanism is also presented. The experimental results suggested that the co-reactants have a different ECL behaviour compared to TPA, such as different pH- and surfactant-responses. The detection limits of Ru(bpy)32+ using NTA, EDTA and HEDTA as co-reactants are 1, 60 and 680 fmol·L-1, respectively. The results indicate that NTA has a much higher efficiency than TPA to excite Ru(bpy)3 2+ ECL under their own optimal conditions. NTA could be widely used in many fields because it is less toxic, corrosive and volatile than TPA. Moreover, using Ru(bpy)3 2+ ECL, a sensitive method for the detection of aminocarboxylic acids is also developed. An improvement of four orders of magnitude in detection limits is obtained for EDTA compared to the known Ru(bpy) 3 2+ chemiluminescent methods. Due to the highly sensitive electrochemiluminescence (ECL), tris (2,2’-bipyridyl) ruthenium (II) (Ru (bpy) 32+) is often used in the field of bioarrays with the help of co-reactants. However, the Thus, the search for safe, sensitive and economical co-reactants is critical. Herein, three aminocarboxylic acids, ethylenediamine-tetraacetic acid (EDTA), nitrilotriacetic acid (NTA), and 2-hydroxyethylethylene diaminetriacetic acid (HEDTA), have been investigated as potential co-reactants for promoting Ru (bpy) 32+ ECL behavior. A possible ECL mechanism is also presented. The experimental results suggested that the co-reactants The detection limits of Ru (bpy) 32+ using NTA, EDTA and HEDTA as co-reactants are 1, 60 and 680 fmol·L-1 , respectively. The results indicating that NTA has a much higher efficiency than TPA In excite Ru (bpy) 3 2+ ECL under their own optimal conditions. NTA could be widely used in many fields because it is less toxic, corrosive and volatile than TPA. method for the detection of aminocarboxylic acids is also developed. An improvement of four orders of magnitude in detection limits is obtained for EDTA compared to the known Ru (bpy) 3 2+ chemiluminescent methods.