Nano-sized silver particle (<20nm) was highly dispersed on the surface of Li4Ti5O12 particles by an electroless deposition method. The Ag additive played a positive role in improving the electrical contact between Li4Ti5O12 particles and the current collector and therefore improved the high rate capacity of Li4Ti5O12, but it did not take part in the electrochemical reactions with Li+ in Li4Ti5O12/Ag composite during the cycling. The experimental results showed that the smaller the silver particles and the more homogeneous dispersion of silver particles in the Li4Ti5O12 matrix, the better the cycling performance we obtained.