Rational structure design of anode materials plays crucial roles in the continuous improvement of electrochemical lithium storage performance for high performance lithium-ion batteries (LIBs). In this study, a novel hierarchical straw-sheaf-like Co3O4 (Co3O4-SSL) composed of numerous strongly tied nanoneedles was successfully synthesized with hydrothermal route by a charge-driven self-assembly strategy. Material characterizations indicated that typical length of nanoneedles was about 10 mu m and the average diameter was about 80 nm. Mechanism studies implied that positively charged diallyldimethylammonium chloride (DDA) molecules played a key role in the formation of straw-sheaf-like structures. Impressively, when Co3O4-SSL was investigated as anode materials for electrochemical lithium storage, high specific capacity (e.g. 842.9 mAh g(-1) after 300 cycles tested at 500 mA g(-1)), superior cycling stability (e.g. capacity retention of about 100% over 300 cycles) and excellent rate capability (e.g. 707 mAh g(-1) tested at 3000 mA g(-1)) were achieved in the repeated chargingdischarging cycles, demonstrating great potentials in energy storage materials. The proposed synthetic strategy is appealing in electrode structure design for next generation LIBs.