AbstractPreparation of uniform, spherical Li4Ti5O12 with high tap density is significant to achieve a high volumetric energy density in lithium‐ion batteries. Herein, Li4Ti5O12 microspheres with variable tap density and tunable size distribution were synthesized by a newly designed industrial spray‐drying approach. The slurry concentration, sintering time, sintering conditions after spraying, and the effect of lithium/titanium molar ratio on the lithium‐ion (Li+) storage capability were investigated. A narrow particle size distribution of around 10 μm and a 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 a much higher capacity of 168 mAh g−1 at a rate of 1 C and show a 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 lithium‐ion batteries or capacitors; meanwhile, the presented approach is also applicable for preparing other kind of spherical materials.