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 kgtotal −1 (based on the total mass of the TO‐MO and LiCoO2) and excellent energy density (285 Wh kgtotal −1) that is higher than many previously reported metal oxide anode‐based Li full cells. Synergistic TiO2‐MoO3 core–shell nano­wire array anode is developed, showing high capacity (ca. 670 mAh g−1; 3.986 mAh cm−2), excellent cycleability (>200 times), and good rate performance. Ultrahigh energy density (285 Wh kgtotal −1) and power density (1086 W kgtotal −1) are further achieved for a full cell LIB device assembled using the TiO2‐MoO3 hybrid array as anode and commercial LiCoO2 film as cathode.