The charge/discharge characteristics of metal (Cu or Ag) and carbon co-coating spherical porous Li4Ti5O12 are investigated in this paper. And the Li4Ti5O12/C-Ag presents the highest reversible capacity of 189.0 mAh g−1 among the four samples of Li4Ti5O12, Li4Ti5O12/C, Li4Ti5O12/C-Cu and Li4Ti5O12/C-Ag. Furthermore, the charge/discharge tests of the Li4Ti5O12/C-Ag electrode without conductive carbon show low initial reversible capacity of 17.6 mAh g−1 during charge-discharged at 0.1C (1C = 170 mA), suggesting that the conductive carbon is necessary for this kind of active material. The result also shows that a higher reversible capacity of about 110 mAh g−1 can be obtained by decreasing the discharging current density to 0.005C. Based on the low bulk electronic conductivity of Li4Ti5O12 can be improved by lithium insertion, an improved charge-discharge method is developed by discharging the Li4Ti5O12/C-Ag electrode at 0.005C for 20 h to improve its electronic conductivity and further discharge at 0.1C to shorten the discharge time.