The cathode-active materials, layered Li[Ni0.333Co0.333Mn0.293Al0.04]O2−z F z (0≤ z ≤0.1), were synthesized from a sol–gel precursor at 900°C in air. The influence of Al–F co-substitution on the structural and electrochemical properties of the as-prepared samples was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and electrochemical experiments. The results showed that Li[Ni0.333Co0.333Mn0.293Al0.04]O2−z F z has a typical hexagonal structure with a single phase, the particle sizes of the samples tended to increase with increasing fluorine content. It has been found that Li[Ni0.333Co0.333Mn0.293Al0.04]O1.95F0.05 showed an improved cathodic behavior and discharge capacity retention compared to the undoped samples in the voltage range of 3.0–4.3V. The electrodes prepared from Li[Ni0.333Co0.333Mn0.293Al0.04]O1.95F0.05 delivered an initial discharge capacity of 158mAh−1 g and an initial coulombic efficiency is 91.3%, and the capacity retention at the 20th cycle was 94.9%. Though the F-doped samples had lower initial capacities, they showed better cycle performances compared with F-free samples. Therefore, this is a promising material for a lithium-ion battery.