In this study, Cu-doped ZnO aerogel nanoparticles with a 4% copper concentration (Cu4ZO) were synthesized using a sol–gel method, followed by supercritical drying and heat treatment. The subsequent fabrication of Cu4ZO ceramics through Spark Plasma Sintering (SPS) was characterized by X-ray diffraction (XRD), field-emission gun scanning electron microscopy (FE-SEM) equipped with EDS, and impedance spectroscopy (IS) across a frequency range of 100 Hz to 1 MHz and temperatures from 270 K to 370 K. The SPS–Cu4ZO sample exhibited a hexagonal wurtzite structure with an average crystallite size of approximately 229 ± 10 nm, showcasing a compact structure with discernible pores. The EDS spectrum indicates the presence of the base elements zinc and oxygen with copper like the dopant element. Remarkably, the material displayed distinct electrical properties, featuring high activation energy values of about 0.269 ± 0.021 eV. Complex impedance spectroscopy revealed the impact of temperature on electrical relaxation phenomena, with the Nyquist plot indicating semicircular arc patterns associated with grain boundaries. As temperature increased, a noticeable reduction in the radius of these arcs occurred, coupled with a shift in their center points toward the axis center, suggesting a non-Debye-type relaxation mechanism. Dielectric analyses revealed a temperature-driven evolution of losses, emphasizing the material’s conductivity impact. Non-Debye-type behavior, linked to ion diffusion, sheds light on charge storage dynamics. These insights advance potential applications in electronic devices and energy storage.