The compounds LiNi1 –xCoxPO4 (x = 0.3, 0.5, 0.7) have an olivine structure, space group Pnma, in which 3d-transition metal ions are located in the octahedral position 4c. Structural analysis of polycrystalline LiNi1 –xCoxPO4 (x = 0.3, 0.5, 0.7) samples was carried out by elastic neutron scattering, and variations of the mutual distribution of nickel and cobalt ions in the 4c position were studied in detail. For the LiNi0.5Co0.5PO4 compound, six models of the mutual distribution of nickel and cobalt ions were proposed. The best description of neutron diffraction patterns for x = 0.5 composition was obtained for two models of the distribution of Ni and Co ions in the subsequence: Ni–Co–Ni–Co and Co–Ni–Co–Ni, respectively. It is shown that nickel ions form ab planes alternating with cobalt planes in the direction of the c axis in the compound LiNi0.5Co0.5PO4. Four models for the mutual distribution of Ni and Co ions in the 4c position to describe the neutron diffraction patterns for x = 0.3 and x = 0.7 compounds were proposed. The considered four cases for the models of the predominant distribution of Ni/Co ions lead to the appearance of additional structural reflections that are absent in the experimental neutron diffraction patterns. The experimental neutron diffraction patterns of LiNi0.7Co0.3PO4 and LiNi0.3Co0.7PO4 samples are best described using the model of equiprobable distribution of 3d-transition metal ions.