A novel synergistic TiO₂‐MoO₃ (TO‐MO) core–shell nanowire array anode has been fabricated via a facile hydrothermal method followed by a subsequent controllable electrodeposition process. The nano‐MoO₃ shell provides large specific capacity as well as good electrical conductivity for fast charge transfer, while the highly electrochemically stable TiO₂ nanowire core (negligible volume change during Li insertion/desertion) remedies the cycling instability of MoO₃ shell and its array further provides a 3D scaffold for large amount electrodeposition of MoO₃. In combination of the unique electrochemical attributes of nanostructure arrays, the optimized TO‐MO hybrid anode (mass ratio: ca. 1:1) simultaneously exhibits high gravimetric capacity (ca. 670 mAh g⁻¹; approaching the hybrid's theoretical value), excellent cyclability (>200 cycles) and good rate capability (up to 2000 mA g⁻¹). The areal capacity is also as high as 3.986 mAh cm⁻², comparable to that of typical commercial LIBs. Furthermore, the hybrid anode was assembled for the first time with commercial LiCoO₂ cathode into a Li ion full cell, which shows outstanding performance with maximum power density of 1086 W kg_total ⁻¹ (based on the total mass of the TO‐MO and LiCoO₂) and excellent energy density (285 Wh kg_total ⁻¹) that is higher than many previously reported metal oxide anode‐based Li full cells.