In this work, the metal ferrites MFe2O4 (M = Ni, Mn, Cu) were synthesized from metal nitrate precursors by the sol–gel auto-combustion method using diethanolamine (DEA) as a potential fuel. The crystal structures of these ferrite powders were characterized by X-ray diffraction (XRD) technique confirming the complete formation of the single-phase cubic spinel crystal structure. The ferrimagnetism characteristic and the difference of the magnetic properties such as saturation magnetization (Ms), remanent magnetization (Mr), and coercivity (Hc) for each after-calcined ferrite sample were scrutinized through the ferrimagnetic hysteresis loop (M–H) obtained from the vibrating sample magnetometer (VSM) measurement. Moreover, the cation distribution and valence state of these ferrites were investigated by the Ni, Mn, Cu, and Fe K-edge X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectra using the synchrotron radiation light source. From the XAS results, the analyses of both XANES and EXAFS spectra show the existence of accurate oxidation state for transition metal ions and the interionic distance to the nearest neighbors in the spinel crystal structure. In particular, the curve-fitting analysis of Ni, Mn, Cu, and Fe K-edge EXAFS spectra indicates that the degree of inversion in these metal ferrites is entirely different and found to be 0.2 for MnFe2O4, 0.8 for CuFe2O4, and 1.0 for NiFe2O4, which are the important information for understanding their effects on relevant magnetic properties.