Co3O4, as an attractive lithium ion battery anode material, though benefited from its high theoretical capacity, has long suffered from low electrical transportation and dramatic volume variations. Therefore, to develop a LIB anode material with both good capability and excellent stability, rational design of composite material is becoming an appealing method. Herein, we report a scalable method of fabricating integrated Co3O4/TiO2 composite hollow polyhedrons through a cation-exchange approach in metal-organic framework. In this synthesis, well-defined ZIF-67 particles not only serve as the host to accommodate exchanged titanium cations but also the template to form hollow polyhedron structure. The obtained integrated Co3O4/TiO2 composite hollow polyhedrons exhibit a high reversible capacity of 642mAh/g at a rate of 500mA/g after 200 cycles, accounting for 96.9% of the initial capacity, much higher than that of pure Co3O4, which only maintain a specific capacity of 200mAh/g and a capacity retention of 40%. The optimized integrated Co3O4/TiO2 composite hollow polyhedrons display significant improvements in electrochemical performance, demonstrating great potential as advanced anode material for future lithium ion batteries.