摘要： Low band gap polymer complexes are promising due to its flexibility, and exhibiting electronic and optical properties of inorganic semiconductors. The effect of PEG on the physical properties of PVA was evaluated. Then, blend (PVA: PEG = 50:50) doped with rare earth (La or Y) and transition metal (Fe or Ir) chlorides to obtain solid polymer electrolyte films. XRD shows that adding PEG to PVA results in a new peak, 2θ = 23o with increased intensity as PEG ratio increases. However, doping with La3+, Fe3+ or Ir3+ eliminate this peak and decrease the crystallinity. SEM exhibits significant changes in the morphology of films. FTIR confirms miscibility between PVA & PEG and the complexation of the salts. The optical band gap (Eg) of PVA ~ 5.37 eV, decreased slightly by blending with PEG. While it decreased significantly to 2.64 eV and 2.78 eV after doping with Fe3+ or Ir3+. There are a consistency between Eg values obtained by Tauc's model and that obtained from the optical dielectric loss. The dielectric constant and loss, in temperature range 303–405 K & frequency range 1.0 kHz ‐ 5.0 MHz, indicate one or two relaxation peak(s) depending on the film composition. Accordingly, conduction mechanism varied between correlated barrier hopping and large polaron tunneling. The DC conductivity was strongly depend on the dielectric loss. The transition metal salts appear to be more effective than the rare earth ones in increasing σac of films to higher values that candidates them in semiconductors industry.