AbstractThis manuscript focuses on how to improve the electronic conductivity and lithium‐ion diffusivity of Li4Ti5O12 thin films, which present a serious constraint to the development of the solid‐state lithium‐ion batteries. Given this understanding, we have found that creating amorphous structural features and hierarchical channels of thin films form a very simple yet effective approach to solve the problem. The unique structural features and high electrical conductivity of the as‐prepared thin films result in high capacity (283.5 mAh g−1 at 10 μA cm−2) and good cyclic stability (≈3 % capacity loss after 100 cycles at 10 μA cm−2). These important findings could open up new opportunities for Li4Ti5O12 in constructing high‐performance binder‐free energy storage devices.