Herein, we used sol-gel auto combustion technique for fabrication of the series of nickel substituted magnesium-zinc spinel ferrite (Mg0.3NixZn0.7-xFe2O4) nanoparticles by varying nickel concentrations as 0.00 ≤ x ≤ 0.20. X-ray diffraction (XRD) investigation evidenced that the synthesized nanomaterials are of spinel ferrite nature with secondary phase. Moreover, the crystallite size was observed to be in the range from 13 to 17 nm as estimated by Scherrer’s formula. It has been found that the structural parameters (e.g., bulk density, lattice constant, micro strain, crystallite size, surface area etc.) of the as-synthesized magnesium-zinc spinel ferrite nanoparticles have been strongly influenced by doping content of nickel. Moving further, we have investigated the dielectric properties of the prepared nanoparticles in the frequency range from 20 Hz to 20 MHz. The remarkable electric modulus, impedance and dielectric properties of the prepared spinel ferrites made these materials a potential candidate for low- and high-frequency applications.