Titania is considered to be an attractive candidate as anode for sodium ion batteries due to excellent cycle stability, advanced safety features, and small volume deformation in the charge-discharge process. However, limited by sodium storage mechanism, the fast charge and discharge performance of multi-crystals titania is failed to satisfy the requirements of commercial application. Here, we develop a Matryoshka-like carbon nanotubes@anatase nanocrystalline@amorphous carbon (CNTs@aTiO2@C) nanofibers for ultrafast sodium ion storage. A nano-confinement coating strategy is demonstrated for constructing an intermediate layer assembled by ultrafine nanocrystalline (2-3 nm) of anatase. The synthesized Matryoshka-like nanofibers with diameters of ∼95 nm consists of amorphous carbon outer layer (10-13 nm), anatase nanocrystalline assembled intermediate layer (13-15 nm), and carbon nanotube core. Benefit from the ultra-refinement of anatase nanocrystalline and Matryoshka-like micro-morphology, the proportion of the capacitive-controlled contribution are up to 90.1 %, 90.6%, 91.9 %, 92.3%, and 93.6% with sweep rate increased from 0.2 to 0.4, 0.6, 0.8, and 1.0 mV s−1, thus result in an outstanding reversible specific capacities of ∼120 mA h g−1 with Coulombic efficiency of ∼99.5% after long-life of 10000 cycles at ultrafast rate of 10 A g−1.