LiMn2O4 films with vertically aligned holes were formed by electrostatic spray deposition (ESD) and subsequent annealing. Different surface morphologies, such as dense grains, 1μm-diameter pores with 1μm-thick walls, and 5μm pores with 3μm walls, were formed by varying the lithium sources in the precursor solution. The randomly oriented pores in the films prepared using ESD were rearranged in vertical stacks after annealing to produce crystalline LiMn2O4. This process would be suitable for constructing three-dimensional interfaces between active materials and solid-state electrolytes.