Functional materials with both exposed highly reactive planes and hollow structures have attracted considerable attentions with respect to improved catalytic activity and enhanced electrochemical energy storage. Herein, we report the synthesis of unusual single-crystal Co3O4 nanocages with highly exposed {110} reactive facets via a one-step solution method. When tested as anode materials in lithium-ion batteries, these Co3O4 nanocages deliver a high reversible lithium storage capacity of 864 mAh g(-1) at 0.2C over 50 cycles and exhibit an excellent rate capability. The dominantly exposed {110} planes, a high density of atomic steps in nanocages, and the large void interiors lead to the regarded superior electrochemical performance.