Abstract An electrochemiluminescence (ECL) enhancement method combined with solid-phase extraction has been developed for the determination of melamine in dairy products. It was found that melamine in a strong base solution is able to enhance the ECL of Ru(bpy)32+ at glass carbon electrode. The optimum experimental conditions for the determination of trace melamine by ECL, such as scan mode and scan rate of the applied potential, the type of buffer solutions and their pH conditions, were investigated. Under optimized conditions, the enhanced ECL intensity was linearly proportional to the logarithm of melamine concentration in the range of 0.01–1.0ppb, and the detection limit was 0.003ppb. The method has been successfully demonstrated to determine melamine in dairy products including liquid milk, yogurt and milk powder samples. The relative standard deviations ranging from 5.3% to 11.2% and the recoveries from 95.2% to 102.4% were acquired by this method. A possible mechanism for the ECL enhancement effect was also proposed.