Silver (Ag) nanoparticles were directly electrodeposited on multi-walled carbon nanotubes (MWCNT) in AgNO 3 /LiNO 3 containing EDTA (ethylenediaminetetraacetic acid). The structure and nature of the resulting Ag/MWNT composite were characterized by field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD), and the distribution shape of Ag nanoparticles was found to be dependent on the presence of EDTA. The modified electrode showed excellent electrocatalytic activity to redox reaction of hydrogen peroxide and the mechanism of hydrogen peroxide was partly reversible procession with oxidation and reduction peaks at 0.77 and -0.83 V, respectively. The oxidation and reduction peak currents were linearly related to hydrogen peroxide concentration in the range of 1×10 -6 -3×10 -4 and 1×10 -8 -7×10-4 mol•L -1 with correlation coefficients of 0.996 and 0.986, and 3s-detection limit of 9×10 -7 and 7×10 -9 mol•L -1 .