LiNi0.8Co0.15Al0.05O2 cathode powders with fine size and spherical shape were prepared by solid-state reaction method using the Ni–Co–Al–O precursor powders with fine size and spherical shape. The Ni–Co–Al–O precursor powders with fine size and filled inner structure were prepared by spray pyrolysis from the spray solution with drying control chemical additive (DCCA), citric acid and ethylene glycol. The one LiNi0.8Co0.15Al0.05O2 cathode powder with fine size and spherical shape was formed from the one precursor powder with spherical shape and filled morphology. The mean size of the spherical shape LiNi0.8Co0.15Al0.05O2 cathode powders was 1.1μm. The initial discharge capacity of the LiNi0.8Co0.15Al0.05O2 cathode powders prepared from the spray solution with citric acid, ethylene glycol and DCCA was 200mAhg−1. The cycle properties of the cathode powders prepared from the spray solution with and without additives were compared.