Al-doped LiMn2O4 nanostructures are prepared by a single-step solution combustion method. The phase and vibrational mode of the prepared nanostructures are confirmed by XRD and Raman analyses. The SEM showed nanorod and nanosphere morphologies of the prepared samples. The nanostructures have a high specific surface area of 29.75 m2g−1 and a high specific capacitance of 361 Fg−1, in addition to better cyclic stability and high rate capability of oleic acid-based Al-doped LiMn2O4 electrodes. The nanostructures have a better performance in a stable electrolyte solution, a desirable electrolyte for supercapacitor applications under ambient conditions.