Polycrystalline ferrites having the chemical formula Ni0.65−xZn0.35MgxFe2O4 (0 ⩽ x ⩽ 0.2) were prepared by solid state reaction route in steps of x = 0.04. The effect of incorporation of diamagnetic divalent magnesium at expense of nickel on the structural properties of these ferrites has been studied. The proposed cation distribution was derived from theoretical X-ray diffraction intensity calculations. These intensity calculations were done by varying the concentration of magnesium ions over two sites in the lattice. For a certain amount of magnesium concentration, the calculated and observed X-ray diffraction intensities were found to be in good agreement. Site occupancy of divalent diamagnetic magnesium was established from this cation distribution. The octahedral environment facilitates magnesium to enter the B-site at about 95 % and the remaining 5 % occupy tetrahedral sites (A-sites). The movements of cations between tetrahedral and octahedral sites as a result of magnesium substitution were discussed in the view of structural parameters, such as tetrahedral and octahedral bond lengths, cation-cation and cation-anion distances, bond angles and hopping lengths, which were calculated using experimental lattice constants and oxygen parameters. All structural parameters showed slight deviations from ideal values. Among all magnesium substituted samples, the ones with x = 0.12 exhibited insignificant variation in view of structural properties. Dielectric measurements were conducted at a standard frequency of 1 kHz. Large values of the recorded dielectric constants displayed typical characteristics of bulk ferrites. Both dielectric constant and loss values showed mixed variations, attributed to the loss of zinc ions during the sintering process.