Homogeneous nanoparticles of Li4Ti5O12 are prepared by solid-state method assisted with codoping of Mg and Zr. In this present study, orthogonal test is taken and the optimal case is Li3.9Mg0.1Ti3.95Zr0.05O12 heated at 750 degrees C for 10 h. We find temperature and Mg ions are the more powerful factors on particles size and morphology. The results show Li3.9Mg0.1Ti3.95Zr0.05O12 have the most fine particles with diameters distributed in the range of 10-100 nm and have relatively good rate capacity and cycling stability. Moreover, Li3.9Mg0.1Ti3.95Zr0.05O12 first discharge capacity is 186.6 mAh g(-1) at 0.57C, the pure Li4Ti5O12 is 164.7 mAh g(-1) at 0.57C. The electrochemical of Li3.9Mg0.1Ti3.95Zr0.05O12 improved obviously.