A novel series of Cu(II) complexes of azorhodanine derivatives [CuL_n(OAc)(OH₂)]2H₂O (n = 1, R = OCH₃; n = 2, CH₃; n = 3, H; and n = 4, NO₂) have been synthesized. The alternating current conductivity (σ_ac) and dielectric properties of Cu(II) complexes of azorhodanine derivatives were investigated in the frequency range 0.1-100 kHz and temperature range 303-600 K. The values of the thermal activation energies of electrical conductivity ΔE₁ and ΔE₂ for all Cu(II) complexes [CuL_n(OAc)(OH₂)]2H₂O were calculated at different frequencies. The conductivity depends on the substituents of the complexes. The correlated barrier hopping (CBH) is the dominant conduction mechanism for complexes [CuL_n(OAc)(OH₂)]2H₂O (n = 1, 2 and 4) while for complex [CuL₃(OAc)(OH₂)]2H₂O the small polarons tunneling (SPT) is the dominant conduction mechanism.