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Double perovskites are an emerging class of functional materials with a great deal of durability perspective owing to their inherent flexibility in cation coordination selection. Here, we synthesized pristine and Cu²⁺-doped Ba₂NiWO₆ utilizing the solid-state reaction route to investigate their structural, morphological, and dielectric behavior. Structural examination revealed the development of a cubic crystal structure for both compositions, and Cu²⁺ integration in Ba₂NiWO₆ decreases the crystallite size. The spherical-shaped grains shrink in size and start agglomeration with Cu²⁺ incorporation. The incorporation of Cu²⁺ reduces the grain size, leads to accumulation of space charges at the grain boundaries, and thus, facilitates growth in the space charge polarization. This increases the dielectric constant of the material, thus making these compositions viable for advanced miniaturized electronic devices.