Multilayered porous ultralong LiMn2O4 nanorods with a length of 30 μm, a diameter of 900 nm have been synthesized by using the ultralong γ-MnOOH as a self-sacrifice template, which is involved in the dissolution, regrowth and self-assembly process. Galvanostatic charge and discharge measurements show that the multilayered porous ultralong LiMn2O4 nanorods exhibit superior rate, specific capacity, long cycle stability and excellent high temperature performance. It delivers an initial charge and discharge specific capacity of 137.5 mAh g−1 and 134 mAh g−1 at 0.2C rate. Importantly, the multilayered porous ultralong nanorod structures are well preserved after prolonged charge and discharge cycling (1000 cycles) at a relatively high rate of 2C, 3C and 5C, demonstrating the excellent structural stability of the as-synthesized LiMn2O4, as is confirmed from scanning electron microscope images after several hundred cycles. Moreover, even at an extremely high rate of 50C, it still delivers a capacity of 75.4 mAh g−1. The long cycle life, excellent high temperature and superior rate, and specific capacity performance are attributed to its ultralong and one-dimensional porous nanostructure, respectively.