​The permittivity and conductivity relaxation processes of polyethylene oxide (PEO) composite along with potassium hexachloroplatinate (K₂PtCl₆) electrolytes additive forming PEO/K₂PtCl₆ complex composite have been investigated. The complex composite has been used as a model for dry‐polymer electrolytes (PEs) due to the fact that, the anion is large enough for mimicking the immobilized anion in real dry‐polymer electrolytes. Stand‐free composite films with 0%, 1%, 3%, and 5% concentrations of K₂PtCl₆ have been studied using broadband dielectric spectroscopy in the temperatures range from 150 K until 345 K. The microstructural dynamics revealed the α‐, β‐, and σ‐relaxations and their salient spectral characteristics at various concentrations of K₂PtCl₆ in PEO. The experimental ε” master curves were fitted to HN function for one and/or two relaxation peaks with and without the electrical conductivity …​​