Preparation of uniform spherical Li4Ti5O12 with high tap density is significant to achieve a high volumetric energy density in lithium-ion batteries. Herein, Li4Ti5O12 micro-spheres with variable tap-density and tunable size distribution were synthesized by a newly designed industrial spray drying approach. The slurry concentration, sintering time and sintering conditions after spray, the effect of Li/Ti molar ratio on the lithium ion (Li+) storage capability were investigated. A narrow particle size distribution around 10 μm and high tap-density close to 1.4 g cm-3 of the Li4Ti5O12 spheres can be obtained under the optimized conditions. The Li4Ti5O12 spheres can deliver much higher capacity of 168 mAh g-1 at 1 C-rate and show high capacity retention of 97.7% over 400 cycles. The synthetic conditions are confirmed to be critical for improving the electron conductivity and Li+ diffusivity by adjusting the crystal and spatial structures. As-prepared high performance Li4Ti5O12 is an ideal electrode for Li-ion batteries or capacitors; meanwhile the presented approach is also applicable for preparing other kind of spherical materials.