CoO nanostructures have been extensively studied as anode materials for rechargeable lithium-ion batteries (LIBs) because of their stability and high energy density. However, several drawbacks including low electrical transport and severe volume changes over a long period of operation have limited their utilities in LIBs. Rational composite design is becoming an attractive strategy to improve the performance and stability of potential lithium-ion-battery anode materials. Here, a simple method for synthesizing hollow CoO@TiO nanostructures using metal-organic frameworks as sacrificial templates is reported. Being used as an anode material for LIBs, the resulting composite exhibits remarkable cycling performance (1057 mAh g at 100 mA g after 100 cycles) and good rate performance. The optimized amorphous CoO@TiO hollow dodecahedron shows a significant improvement in electrochemical performance and shows a wide prospect as an advanced anode material for LIBs in the future.