​Polyethylene oxide (PEO) complexed with molecular iodine (I₂) forming PEO/I₂ complex composites stand‐free films were investigated using dielectric relaxation, X-ray photoelectron spectroscopy (XPS), UV–Vis spectrophotometry, structural and morphological techniques. Scanning electron microscopy was used to monitor the variation in the surface morphology and the related roughness. 2D Energy-dispersive X-ray spectroscopy (EDX) measurements enabled to observe the distribution of iodine on the film surface. High resolution XPS measurements were used to define the iodine anion types and the metallic iodine existence, as well as the relevant concentrations based on the binding energies. The dielectric relaxation measurements were carried out over the frequency range from 0.1 to 10⁷ Hz and temperature range from 155 to 330 K. Dielectric loss (ε′′) curves were fitted to the Havriliak–Negami …​