The present paper details the way to determine the cation distribution in mixed oxides with transition ions from the diffraction and magnetic susceptibility data. This approach allows one to determine phase abundances and phase compositions by two combined procedures. By X-ray diffraction Rietveld pro-file refinement and magnetic susceptibility data analysis it is possible to estimate the ratio and the oc-cupancy factor of paramagnetic ions in different oxidation states. A brief discussion of practical cases is reported. In the Li-Ni-0 system the lithium cationic fraction of the ordered phase Li 2r Ni2_2 X 0 2 in-creases monotonically with the total lithium fraction x, for 0.31 < x, < 0.46. In the Li-Mn-0 system for 0.36 < JC, < 0.53 the Li 2 Mn0 3 fraction has been determined, and for the coexistent Li [Li-y Mn 2 _ > ,] 0 4 spi-nel phase the dependence of y on x t has been evaluated.