<p>TiNb₂O₇ represents an up-and-coming anode material for fast-charging lithium-ion batteries, but its practicalities are severely impeded by slow transfer rates of ionic and electronic especially at the low-temperature conditions. Herein, we introduce crystallographic engineering to enhance structure stability and promote Li⁺ diffusion kinetics of TiNb₂O₇ (TNO). The density functional theory computation reveals that Ti⁴⁺ is replaced by Sb⁵⁺ and Nb⁵⁺ in crystal lattices, which can reduce the Li⁺ diffusion impediment and improve electronic conductivity. Synchrotron radiation X-ray 3D nano-computed tomography and in situ X-ray diffraction measurement confirm the introduction of Sb/Nb alleviates volume expansion during lithiation and delithiation processes, contributing to enhancing structure stability. Extended X-ray absorption fine structure spectra results verify that crystallographic engineering also increases short Nb-O bond length in TNO-Sb/Nb. Accordingly, the TNO-Sb/Nb anode delivers an outstanding capacity retention rate of 89.8% at 10 C after 700 cycles and excellent rate performance (140.4 mAh g⁻¹ at 20 C). Even at −30&#xa0;°C, TNO-Sb/Nb anode delivers a capacity of 102.6 mAh g⁻¹ with little capacity degeneration for 500 cycles. This work provides guidance for the design of fast-charging batteries at low-temperature condition.</p>