Two copper-ion conducting solid-polymer electrolyte systems based on polyacrylonitrile (PAN) have been synthesized and characterized using DC polarization tests and impedance measurements. The system with 21 mol% PAN: 30 mol% EC: 45 mol% PC: 04 mol% CuCNS has a room temperature conductivity of 3.30×10−5 S cm−1 and an activation energy of 0.25 eV. The conductivity versus temperature plot obeys an Arrhenius type variation. It is predominantly an ionic conductor with negligible electronic conductivity. It has a high anionic transference number (t −=0.80) due to CNS− ions and a low cationic transference number (t +=0.20) due to Cu+ ions. The system with 20 mol% PAN: 41 mol% EC: 34 mol% PC: 5 mol% CuTf has a room temperature conductivity of 4.10×10−3 S cm−1 and an activation energy of 0.14 eV. It obeys the VTF equation. The system appears to be a mixed conductor with a cationic (Cu2+/Cu+) transference number of t +=0.50 and an electronic transference number of t e=0.50 with negligible anionic conductivity. Both systems yielded free standing stable polymer electrolyte films.