This paper reports an enhanced retention rate of LiNi0.8Co0.15Al0.05O2 (NCA) cathode material for Li-ion batteries synthesized with glycerol as a solvent and a reactant. Glycerol is a fuel and the heat released during synthesis could be considered as an additional free energy source for material preparation. Scanning electron microscopy (SEM) images and X-ray diffraction (XRD) results show an early stage of crystallization of the produced powder. Early crystallization in the NCA material at low temperatures was believed to hinder cationic mixing that would occur at higher temperatures during calcination. As a result, cycling of the NCA material shows a very stable capacity. The NCA material displays 97% capacity retention at 1C (1C = 200 mA/g) after 50 cycles, 87.6% at 0.3C after 100 cycles, and 93.6% at 0.1C after 70 cycles, which are better than those reported previously.