Lithium-ion batteries with green and inexpensive aqueous electrolytes solve the safety problem associated with conventional lithium-ion batteries that use highly toxic and flammable organic solvents, which usually cause fires and explosions. However, the relatively low capacities (usually<65mAhg−1) and less than 50% capacity retention over 50 cycles unfortunately limit their promising applicability. Herein, a novel model of ordered lamellar organic–inorganic hybrid nanorods is first put forward as an excellent platform to circumvent the above issues. Taking the synthetic highly ordered lamellar V2O3-based hybrid nanorods as an example, they deliver a capacity up to 131mAhg−1, nearly 1.5 and 2 times higher than that of 10-nm V2O3 nanocrystals (90mAhg−1) and 2-μm bulk V2O3 (73.9mAhg−1). Also, their excellent cyclability of 88% after 50 cycles is remarkably better than that of 10-nm V2O3 nanocrystals (64%) and 2-μm bulk V2O3 (41%). This work provides a facile route for gram-scale synthesizing highly ordered lamellar hybrid materials and proves that these unique structures are excellent platforms for significantly improving aqueous lithium-ion battery performances especially at high discharge rates, giving tantalizing perspectives in future design and synthesis of high-performance active materials for aqueous lithium-ion batteries.