High-power,　fast-charging　capability　is　an　urgent　issue　for　the　development　of　advanced　Li-ion　batteries　(LIBs)　for　electrified　mobility　applications.　An　anatase　titanium　oxide　mesocrystal　(TOM)　Li-ion　battery　(LIB)　anode　comprising　extremely　small　(3–5　nm)　and　crystallographically　coherent　nanocrystallite　subunits　demonstrate　a　high　specific　capacity　(up　to　225　mAh　g-1)　and　extraordinary　rate　capability　and　cycle　stability　under　stressful　currents　(83　%　capacity　retention　after　9000　cycles　at　10　C　rate,　1　C　=　168　mA　g-1),　considerably　outperforming　the　conventional　nanocrystalline　titanium　oxide　(TO)　electrode.　The　investigation　of　the　underlying　(de)lithiation　mechanism　using　synchrotron　X-ray　analyses　and　density　functional　theory　calculations　reveals　a　novel　crystalline–amorphous–crystalline　pathway　for　TOM　involving　an　amorphous　phase　existing　within　a　Li　stoichiometry　range　approximately　LixTiO2,　x　=　0.2–0.9.　The　combination　of　structure　amorphization　and　existing　of　a　fast　inter-grain　diffusion　network　inherent　to　the　hierarchical　interior　of　mesocrystal　empowers　the　TOM　electrode　with　orders-of-magnitude　higher　diffusion　rates　as　compared　with　the　TO　electrode.　The　single-crystal-like　crystallographic　coherence　of　the　(de)lithiation　end-products　enables　favorable　chemo-mechanical　stability　to　avert　particle　cracking　during　high-rate　cycling.　The　study　indicates　a　potential　new　direction　for　engineering　cycle-stable　fast-charging　electrode　materials.　©　2022　Elsevier　Ltd