The electrochemical performances of lithium‐ion batteries (LIBs) will be significantly degraded under low‐temperature conditions, which restricts their wide application in cold environments. Herein, the low‐temperature transport kinetics of a novel Nb1.94Mo0.06O5@C nanocomposite anode is accelerated greatly via engineering the microstructure and NbO6 octahedron. The detailed crystallographic features are characterized by using synchrotron radiation, spherical electron microscope, and density functional theory simulation methods. Both experimental and simulation analysis suggest that Mo6+ preferentially replaces Nb5+ in the regular octahedral location and distorts the NbO6 octahedron, resulting in a widened c‐axis spacing and a lowered ion diffusion barrier. Coupled with the enhanced electronic conductivity derived from surface carbon layer, Nb1.94Mo0.06O5@C anode exhibits an enhanced charge transfer process, improved Li+ diffusion kinetics, pronounced pseudo‐capacitance process, and excellent low temperature capacity. Furthermore, in situ X‐ray diffraction and ex situ electron microscope elucidate that the structural evolution of Nb1.94Mo0.06O5@C is highly reversible, unveiling its excellent cycling stability. The full cell assembled with LiNi0.6Co0.2Mn0.2O2 cathode demonstrates excellent practicality. This study reveals the critical role of distorting NbO6 octahedron and expanding crystal spacing in facilitating rapid Li+ diffusion and enhancing charge storage performance of Nb2O5 at low temperatures.