Li4Ti5O12 has been considered as a promising electrode material for lithium secondary batteries. In this work a spray drying process was developed to prepare porous and spherical Li4Ti5O12 powders with Li2CO3 and rutile type TiO2 as precursors and PVB as forming agent of pores. The experimental results showed that porous and spherical morphology of the spray-dried powders was maintained during the sintering and the subsequent heat treatment. The oxygen atmosphere was demonstrated important to the electrochemical performance of the Li4Ti5O12 powders. However, overtime heat treatment would result in superfluous loss of lithium content and therefore led to obvious decrease of charge and discharge capacities.