Due to their uncontrollable assembly and crystallization process, the synthesis of mesoporous metal oxide single crystals remains a formidable challenge. Herein, we report the synthesis of single-crystal-like mesoporous Li₂TiSiO₅ by using soft micelles as templates. The key lies in the atomic-scale self-assembly and step-crystallization processes, which ensure the formation of single-crystal-like mesoporous Li₂TiSiO₅ microparticles via an oriented attachment growth mechanism under the confinement of an in-situ formed carbon matrix. The mesoporous Li₂TiSiO₅ anode achieves a superior rate capability (148 mAh g⁻¹ at 5.0 A g⁻¹) and outstanding long-term cycling stability (138 mAh g⁻¹ after 3000 cycles at 2.0 A g⁻¹) for lithium storage as a result of the ultrafast Li⁺ diffusion caused by penetrating mesochannels and nanosized crystal frameworks (5–10 nm). In comparison, bulk Li₂TiSiO₅ exhibits poor rate capability and cycle performance due to micron-scale diffusion lengths. This method is very simple and reproducible, heralding a new way of designing and synthesizing mesoporous single crystals with controllable frameworks and chemical functionalities.

https://doi.org/10.1093/nsr/nwae054