<p>This study aims to analyse the structural and electrical properties of Zn₇Sb₂O₁₂ ceramics at different calcination temperatures. The ceramic was calcined in air at 1000, 1100 and 1200&#xa0;℃ for 2&#xa0;h. The structural and electrical properties of Zn₇Sb₂O₁₂ ceramics were studied via the X-ray diffraction (XRD), current–voltage (I-V) measurements and an impedance analyzer. According to the obtained XRD patterns, the formation of single-phase Zn₇Sb₂O₁₂ was completed at the calcination temperature of 1200&#xa0;℃. The ceramic calcined at 1200&#xa0;℃ showed a nonlinear coefficient of 15.81, a breakdown voltage of 74.0 V/mm and a leakage current of 9.6&#xa0;μA, indicating the excellent stability due to the high density and relatively superior V-I characteristics. At lower frequencies the dielectric constant decreases and the dielectric loss decreases with increasing calcination temperature. The increase in the radius of circular arc with the increasing of calcination temperatures in the Nyquist plots indicates the increase from in R_gb (grain boundary) and the decrease from 6.99 × 10^–10 to 1.33 × 10⁻¹⁰F in capacitance. Electrical conductivity measurements were made over the temperature range of 20–400&#xa0;℃. The electrical conductivity of all samples increased with the measured temperature and was associated with an increase in the activation energy from 1.08 to 1.22 eV.</p>