Thermal and electrical properties of copper oxide doped BiNbO₄ ceramics as well as its spectral characteristics and microstructure were studied in this work. According to XRD, the samples calcined at 950 °C and 1100 °C had the structure of α-BiNbO₄ in spite of the phase transition α→γ(β) at 1040 °C. The studied composite samples had the composition of BiNb_1-хCu_х-yO_4-δ·yСuO (х≤0.04) and were characterized by the graphite color and visually pronounced grain microstructure. The DSC-curves of the samples revealed the reversible endo-effect near 900 °C associated with copper (II) oxide decomposition and the thermal effects caused by the chain of reconstructive phase transitions α→γ→β’→β in BiNb_1-хCu_х-yO_4-δ. It was established that the presence of copper oxide additive in the samples increased the density of the ceramics, on average, by 8–10% and had a thermostatic effect on the compacted samples manifested in the increase in the α→γ(β) phase transformation temperature by ∼ 100 °C. The mass spectrum of vapor over the BiNb_1-хCu_х-yO_4-δ·yСuO samples in vacuum has shown the ionic currents of Bi⁺ and O₂⁺. The absence of Cu⁺ ions in the mass spectrum of vapor was due to low partial pressure of copper vapor. The comparison of the Cu2p-NEXAFS spectra of copper oxides (I) and (II) and BiNb_1-хCu_х-yO_4-δ·yСuO, synthesized at 950 °C and 1100 °C allowed to conclude that copper atoms were in the Cu(II) state in the studied ceramics. The impedance spectroscopy showed that an increase in the copper content reduced the conductivity of the samples synthesized at 950 °C and increased the conductivity of the samples synthesized at 1100 °C. A threefold increase in the copper content led to an increase in low-frequency dielectric losses by 20% in the samples synthesized at 1100 °C. The growth of the capacity of the samples with decreasing frequency indicated the ion-migration nature of polarization.