A templating method is developed to produce porous nanocrystalline anatase materials for negative electrodes in lithium-ion batteries (LIBs). Amphiphilic diblock copolymers are used to generate template films with phase-separated internal structure. Subsequent swelling with acidified titanium(IV) bis(ammonium lactato) dihydroxide (TALH) solution yielded structured hybrid films. Upon heating, the formation of TiO2 nanocrystals is induced, resulting in a three-dimensional mesoporous structure directed by the bulk morphology of the polymer template. In comparison to commercial nanosized anatase, the structured anatase shows significant performance improvements in lithium-ion coin cell batteries in terms of capacity, stability, and rate capability. (c) 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1890-1896