This study investigates the effect of sintering temperature on the structural and electrical properties of co-precipitated nickel stannate (NiSnO3) nanopowder. Sintering temperatures, determined using Thermo Gravimetric Analysis (TGA), reveal a pure hexagonal perovskite structure through X-ray diffraction (XRD) analysis. Crystallite size increased from 10.56 nm to 26.04 nm and lattice strain decreased from 23.05×10−3 to 2.35×10−3 with higher sintering temperatures, analyzed via the Scherrer formula. d-spacing values from SAED patterns align with XRD results, and TEM analysis shows particle size growth from ∼11.43 nm to ∼28.16 nm as sintering temperature rises from 600°C to 900°C. Elemental composition has been confirmed through EDX, and elemental mapping analysis. Impedance spectroscopy via Cole-Cole plots indicated non-Debye-type or multiple relaxations with depressed semicircles due to grain and grain boundary effects. The sample sintered at 900°C exhibits the highest conductivity (8.35×10−5 Ω−1cm−1) with lowest activation energy of 0.31 eV and maximum dielectric constant values, with a minimum relaxation time of 0.00029 sec. Also the frequency variation of Z′′ and M′′ confirm the presence of non-Debye type relaxation. Scaling behavior of the imaginary part of complex impedance and conductivity spectra confirms temperature-independent conduction and relaxation mechanisms. These materials are used in energy storage applications.