In order to find the ideal carbon chain linkage number n for achieving the highest ECL in bimetallic ruthenium tris-bipyridyl complexes, a series of novel complexes [(bpy)₂Ru(bpy′)(CH₂)_n(bpy′)Ru(bpy)₂]⁴⁺ (1, where bpy is 2,2′-bipyridyl, n = 10, 12, 14) for a coreactant electrochemiluminescence (ECL) system have been synthesized. Their ECL properties at a Au electrode have been studied in 0.1 M phosphate buffer by using tripropylamine (TPrA), 2-(dibutylamino)ethanol (DBAE) and melamine as the coreactant, to compare with that of the previously reported bimetallic ruthenium analogous complex [(bpy)₂Ru(bpy′)(CH₂)₈(bpy′)Ru(bpy)₂]⁴⁺. The results demonstrate that the ECL intensity depends largely on the length of the saturated carbon chain linkage number n. The highest ECL is reached when n = 10, suggesting that a synergistic effect on ECL enhancement co-exists between the two intramolecular linked ruthenium activating centers. Density functional theory (DFT) calculation demonstrated that the optimized bond distances between Ru and N(bpy′) are the longest both in the ground and the excited triplet states in the case of n = 10, while those for Ru and N(bpy) are the shortest in the excited triplet states. All these factors may be responsible for the above mentioned results. This study provided a methodology to further improve and tune ECL efficiency by using bimetallic ruthenium complexes linked by a flexible saturated carbon chain.