Abstract: β-cyclodextrin modified glassy carbon electrode (β-CD/GCE) was prepared by drop coating method. The electrochemical and electrochemiluminescence (ECL) behaviors of luminol on β-CD/GCE were studied. The optimal modification amount of β-cyclodextrin and the pH value of working solution were determined. The results show that β-CD/GCE can obviously enhance the ECL intensity of luminol compared with a bare electrode. The ECL intensity of luminol is enhanced at the β-CD/GCE when dicyandiamide is added to the system solution. Under the optimal experimental conditions that the modification amount of β-CD is 8 μL and pH value of working solution is 7.4, the ECL intensity changes linearly with the logarithm of the dicyandiamide concentration in the range of 1.0×10^-5~1.0×10^-3 mol/L, indicating that the dicyandiamide can be detected by luminol ECL at β-CD/GCE.