To develop quick‐charge sodium‐ion battery, it is significant to optimize insertion‐type anode to afford fast Na+ diffusion rate and excellent electron conductivity. First‐principles calculations reveal the TiO subcompound superiority for Na+ diffusion following Ti(II)O > Ti(III)O > Ti(IV)O. Hence, in situ growth of amorphous TiO subcompounds with rich oxygen defects based on Ti3C2Tx‐MXene is developed. Meanwhile, the composite presents expanded MXene interlayer spacing and much enhanced conductivity. The synergistic effect of enhanced electron/ion conduction gives a high capacity of 107 mAh g−1 at 50 A g−1, which gives 50% and 150% increasements compared with one counterpart without valence adjustment and another one without MXene expansion. It only needs 20 s (at 30 A g−1) to complete the discharge/charge process and obtains a capacity of 144.5 mAh g−1, which also shows a long‐term cycling stability at quick‐charge mode (121 mAh g−1 after 10000 cycles at 10 A g−1). The enhanced performance comes from fast electron transfer among TiO subcompounds contributed by rich‐defect amorphous TiO2–x, and a reversible change of elastic MXene with interlayer spacing between 1.4 and 1.9 nm during Na+ insertion/extraction process. This study provides a feasible route to boost the kinetics and develop quick‐charge sodium‐ion battery. The composite of elastic S‐doped Ti3C2Tx MXene with 18.2% expanded interlayer spacing and amorphous TiO2–x gives a specific capacity of 121 mAh g−1 at 10 A g−1 after 10 000 cycles, showing great potential in developing functional fast‐charge sodium‐ion batteries. The fast Na+ storage kinetic process and stability comes from optimized insertion‐type MXene and fast electron transfer among TiO subcompounds.