Pristine Li 1−z Ni 1+z O 2 (z=0.02, 0.07, and 0.25) and deintercalated Li x Ni 1.02 O 2 (x=0.82 and 0.63) phases were characterized by neutron diffraction. In all cases, the amount of nickel in the lithium sites was found to be identical to that deduced from X-ray diffraction experiments. The sensitivity of the neutron studies allowed us to show that no lithium ions are in the NiO 2 slabs for z=0.02 and 0.07. A Li/Ni mixing appears only for the most lithium-deficient phase leading to the [Li 0.73 Ni 0.27 ] 3b [Ni 0.98 Li 0.02 ] 3a O 2 cationic distribution for the Li 0.75 Ni 1.25 O 2 phase. Determination of the anisotropic atomic displacement parameters confirms the results previously obtained from EXAFS data. The structural characterization of partially deintercalated phases was in good agreement with the XRD analysis. However, in the case of Li 0.63 Ni 1.02 O 2 , it gave evidence for the presence of a small amount of rhombohedral phase due to fluctuations in the composition of the starting material.