The powders of Li4/3Ti5/3O4/Ag composite were prepared by sol-gel technique. Phase identification, surface morphology and electrochemical properties were studied by X-ray diffraction, scanning electron microscopy, galvanostatic charge-discharge experiments, and electrochemical impedance spectroscopy. The results show that the Ti-O band is not affected by the addditive of Ag. Li4/3Ti5/3O4/Ag and Li4/3Ti5/3O4 have very similar crystal lattice parameters. Ag does not enter the Li4/3Ti5/3O4 crystal and disperses homogeneously in Li4/3Ti5/3O4 particles. Compared with Li4/3Ti5/3O4, Li4/3Ti5/3O4/Ag composite has higher specific capacity, higher columbic efficiency and lower polarization. The additive of Ag have little effect on the lithium ion diffusion of Li4/3Ti5/3O4. The capacity loss of Li4/3Ti5/3O4/Ag is smaller than that of i4/3Ti5/3O4 during cycling. The additive of Ag greatly improves the cycleability of Li4/3Ti5/3O4 powders, especially at higher charge-discharge rate.