Layered Li-rich Mn-based oxides are believed to be a good candidate for cathode material in the next generation of lithium-ion batteries. However, they have some disadvantages, such as low initial coulombic efficiency, low rate capacity, and deficient cyclability. To overcome these shortcomings, various approaches, such as elemental doping, have been adopted. In this study, Al-doped Li1.21Mn0.54Ni0.125Co0.125O2 were successfully synthesized using the sol–gel method. Samples were characterized by thermal analysis (TGA/DTA), X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), surface-area analysis, field emission scanning electron microscopy and transmission electron microscopy (TEM). Measurements of galvanostatic charge discharge and electrochemical impedance spectroscopy were also performed to evaluate the electrochemical performance of the prepared samples. The XRD patterns showed that all the samples with the structure of 0.55Li2MnO3.0.45LiNi0.33Mn0.33Co0.33O2 had a composite material with two individual layered structures that are integrated with each other. By doping Al, the lattice parameters of the samples changed. The first discharge capacity of the Al-doped specimens was lower than that of the pristine sample. In cycling performance results, it is clear that cyclic behavior and capacity stability rate in doped samples have improved compared to the undoped sample, and in the meantime, the sample with 0.05 aluminum doping has shown the best performance. Optimal performance of the doped specimens can be related to lower load transfer resistance and better structural stability.