TiO 2 films of varying thicknesses (up to ≈1.0 µm) with vertically oriented, accessible 7-9 nm nanopores are synthesized using an evaporation-induced self-assembly layer-by-layer technique. The hypothesis behind the approach is that epitaxial alignment of hydrophobic blocks of surfactant templates induces a consistent, accessible mesophase orientation across a multilayer film, ultimately leading to continuous, vertically aligned pore channels. Characterization using grazing incidence X-ray scattering, scanning electron microscopy, and impedance spectroscopy indicates that the pores are oriented vertically even in relatively thick films (up to 1 µm). These films contain a combination of amorphous and nanocrystalline anatase titania of value for electrochemical energy storage. When applied as negative electrodes in lithium-ion batteries, a capacity of 254 mAh g −1 is obtained after 200 cycles for a single-layer TiO 2 film prepared on modified substrate, higher than on unmodified substrate or nonporous TiO 2 film, due to the high accessibility of the vertically oriented channels in the films. Thicker films on modified substrate have increased absolute capacity because of higher mass loading but a reduced specific capacity because of transport limitations. These results suggest that the multilayer epitaxial approach is a viable way to prepare high capacity TiO 2 films with vertically oriented continuous nanopores.insertion of Li + between two electrodes with simultaneous removal and addition of electrons to store or release electrical energy. [2] However, the performance of LIBs depends strongly on the electrode materials and their interaction with the electrolyte. [3] Although many high capacity LIB negative electrode materials are available including Si, Ge, and Sn, they cannot be used in bulk form due to their low range of operating voltage, high stress generated by intercalation of Li + , and the consumption of Li + by unstable solid-electrolyte interface layers during cycling. [4] TiO 2 is a suitable candidate for negative electrodes in LIBs for applications requiring high rate performance and high electrolyte solution stability. [5] Although the theoretical capacity of TiO 2 (330 mAh g −1 ) [6] is lower than that of Sn, Si, or graphite, TiO 2 negative electrodes offer better safety, [6,7] which is one of the major criteria for practical use of batteries. [1b] The relatively high Li + discharge voltage plateau (1.7 V) of TiO 2 avoids the formation of solid-electrolyte interphase layers and electroplating of Li + during cycling. [8] TiO 2 also possesses low volume expansion during Li + insertion, and therefore low strain, which makes it less susceptible to structural deformation and the associated loss of performance on cycling. [6] However, the major barrier in using bulk TiO 2 in LIBs is its poor Li + ionic and electrical Nanoporous Films [+] Present address: Intel Corp.,