Interactions between metal nanoclusters and tertiary amine compounds are demonstrated to generate and strengthen the near infrared electrochemiluminescence (ECL) and current signals upon electrode activation. The catalytic effects of aqueous soluble gold nanoclusters (Au NCs) on the oxidation of prototype tertiary amine are firstly established in solution measurements with the materials system of Au₂₂ lipoic acid (Au-LA) nanoclusters and a common pH buffer HEPES. The near IR ECL and current signals are correlated by potential scanning and step methods under systematic varied HEPES and nanocluster concentrations. Strategies to deposit the nanoclusters on electrode surface are developed to improve the signal and enhancement for future applications. The deposition strategies are further applied to prepare surface assemblies of organic soluble bimetallic Au_25-xAg_x nanoclusters with controlled morphology and coverage. Piperazine derivative drug cetirizine is found to enhance ECL signals from this bimetallic nanocluster-functionalized electrode devices that can be further developed for sensing applications.