Li4Ti5O12 and Al3+ doped Li(4−x/3)Al x Ti(5−2x/3)O12 (x = 0, 0.01, 0.05, 0.1, 0.15, 0.2) are synthesized at 750, 850, 950 °C via solid state reaction using TiO2-rutile, Li2CO3 and Al2O3 as precursors. The samples at 850, 950 °C have better phase purity than those at 750 °C. The preliminary charge–discharge cycling test of undoped and Al3+ doped Li4Ti5O12 reveals that the electrochemical performance of the electrode prepared at 850 °C is better than that at 750, 950 °C. Therefore, the optimum calcination temperature is found to be 850 °C. Li(4−x/3)Al x Ti(5−2x/3)O12 (x = 0.01, 0.05, 0.1), which is the low Al-doped sample, exhibits a higher discharge capacity and rate performance than the high Al-doped Li4Ti5O12 (x = 0.15, 0.2) sample. The first discharge capacities at 0.2, 0.5, and 1 C are 174.4, 161.9, and 153.8mAhg−1, respectively for Li(4−x/3)Al x Ti(5−2x/3)O12 (x = 0.1). These values are similar to those of Li(4−x/3)Al x Ti(5−2x/3)O12 (x = 0.01, 0.05). The capacity retention ratio of Li(4−x/3)Al x Ti(5−2x/3)O12 (x = 0.01, 0.05, 0.1) is over 99.3% after 30 cycles. The capacity increase and good rate performance in the optimum Al-doped Li4Ti5O12 are discussed in relation to the stability of the spinel structure and the resulting ease of lithium insertion.