The optimum coordination structure of Ni–fluoro complexes for the preparation of Ni–Al LDH by LPD process and the diverse anion-exchange properties of as-deposited Ni–Al on α-alumina powder were quantitatively evaluated for the industrial application of new positive material for alkali secondary batteries. The [NiF 6−x−y (NH 3 ) x (OH − ) y ] n+ was more suitable than [NiF 6 ] 4− as the precursor of the deposition of Ni–Al LDH in the LPD reaction, and the improved LPD reaction achieved the synthesis of high purity and high crystallinity Ni–Al LDH. All anion-exchanged Ni–Al LDHs for OH − –, Cl − –, SO 4 2− –, and CH 3 COO − –forms kept the high crystallinity and showed the enlargement of interlayer distances. The tilting angle of the intercalated CH 3 COO − anions was about 15°. Anion-exchange capacity remained constant at a minimum of 0.8 meq g −1 in pH >10, increased as pH decreased, and reached a maximum of 8 meq g −1 at pH 2. Anion-exchange of OH − –form of Ni–Al LDH was accelerated by the neutralization of hydroxide ions in interlayers, in addition, the anion-exchange capacity and the crystallinity of Ni–Al LDH could be controlled by the amount of doped aluminum ions.