Hybrid microwave synthesis has been applied for preparation of Li4Ti5O12, Li2Ti3O7, Li2TiO3 and LiTiO2 for the first time. Stepwise heating was used for avoiding the instantaneous release of gas by-product and obtaining well-shaped samples. The samples were characterized by powder X-ray diffraction, energy-dispersive X-ray analysis and scanning electron microscopy. The obtained samples have relatively uniform particle sizes. The electrochemical performance of Li4Ti5O12 and Li2Ti3O7 were investigated. The first discharge capacity of Li4Ti5O12 was 150mAhg−1 and 141mAhg−1 after 27 cycles and a very flat discharge and charge curve of Li4Ti5O12 was shown at about 1.56V. Similarly, Li2Ti3O7 exhibits good cycle performance. The initial discharge capacity is 118mAhg−1 and 30th cycle is still 112mAhg−1.