High-density Li4Ti5O12 powders comprising spherical particles are prepared by spray pyrolysis from a solution containing dimethylacetamide (drying control chemical additive) and citric acid and ethylene glycol (organic additives). The prepared powders have high discharge capacities and good cycle properties. The optimum concentration of dimethylacetamide is 0.5M. The addition of dimethylacetamide to the polymeric spray solutions containing citric acid and ethylene glycol helps in the effective control of the morphology of the Li4Ti5O12 powders. At a constant current density of 0.17mAg−1, the initial discharge capacities of the powders obtained from the spray solution with and without the organic additives are 171 and 167mAhg−1, respectively.