Nickel substituted Sr–Co nano spinel ferrites with composition Sr0.5-xNixCo0.5Fe2O4 (0.0, 0.1, 0.2, and 0.3) were prepared with the help of a sol-gel auto combustion route. The prepared materials were sintered at 800 for four and a half hours. Analysis of XRD confirmed that the material is composed of a cubic spinel structure with a single phase, and its space group is Fd-3m. Rietveld refinement of X-ray diffraction data was done for all prepared compositions using FULLPROF software. As the composition under study contains more nickel than lattice constant, crystalline size, X-ray density, and bulk density decrease. The dielectric properties were observed about frequency. The dielectric properties revealed that dielectric loss, dielectric constant, and ac conductivity decrease with increasing the Ni2+ content. The activation energy (ΔE) was calculated from the slope of Arrhenius plots. The ΔE found in the range of 0.580–0.096 eV. The analysis of XPS was carried out to examine the elemental state of annealed samples. The prepared material is suitable for employment in applications involving high frequencies because the Ni-doped Sr–Co ferrites with the greatest Ni2+ concentration have the lowest dielectric loss, dielectric constant, and tangent loss value.