LiNi0.5Co0.44Fe0.06VO4 cathode material has been synthesized by a citric acid:polyethylene glycol polymeric method at 723K for 5h in air. The surface of the LiNi0.5Co0.44Fe0.06VO4 was coated with various wt.% of Al2O3 by a wet chemical procedure and heat treated 873K for 2h in air. The samples were characterized by XRD, FTIR, SEM, and TEM techniques. XRD patterns expose that the complete crystalline phase occurred at 723K and there was no indication of new peaks for the coated samples. FTIR spectra show that the complete removal of organic residues and the formation of LiNi0.5Co0.44Fe0.06VO4. TG/DTGA results reveal that the formation of LiNi0.5Co0.44Fe0.06VO4 occurred between 480 and 670K and the complete crystalline occurred at 723K. SEM micrographs show the various morphological stages of the polymeric intermediates. TEM micrographs of the pristine LiNi0.5Co0.44Fe0.06VO4 reveal that the particle size ranged from 130 to 150nm and Al2O3 coating on the fine particles was compact and had an average thickness of about 15nm. The charge–discharge experiments were carried out between 2.8 and 4.9V (versus Li) at a current rate of 0.15C. The 1.0wt.% Al2O3 coated sample had the best electrochemical performance, with an initial capacity of 65mAhg−1 and capacity retention of 60% after 50 cycles. The electrochemical impedance behavior suggests that the failure of pristine cathode performance is associated with an increase in the impedance growth on the surface of the cathode material upon continuous cycling.