Here, we show that a novel 3D woodpile electrode, made from TiO2 nanoparticles using solvent-assisted nanoimprint lithography (NIL), can remarkably enhance both the capacity and power of a lithium-ion battery (LIB). With the convenience of sequential imprinting, woodpile electrodes of different heights are readily made in a “stack-up” manner, resulting in a proportional increase of capacity, which is hard to achieve in thin film batteries. Little evidence of specific capacity decrease was observed as the structure height increased by stacking additional layers. These 3D electrodes boast superior rate performance with 1.5- to 6-fold improvement of the specific capacity (compared to 2D counterpart) during fast cycling (up to 15 C) due to the structure’s large surface area. The TiO2 woodpile proved to be a strong candidate for the anode of a high-performance LIB. More importantly, this work demonstrates the great potential of NIL as a platform to create high density architectures for energy storage devices. The strategy described here can be potentially expanded to other electrochemical systems.