<p>Glasses with the composition (10−<i>x</i>)ZnF₂–50 As₂O₃–40 Sb₂O₃:<i>x</i>Fe₂O₃ (where <i>x</i> varies from 0&#xa0;mol% to 2.5&#xa0;mol% in 0. 5&#xa0;mol% increments) were synthesized. Key physical properties, including molar volume, interionic concentration, ionic distance, polaron radius, electronic polarizability, oxygen packing density, and metallization constant, were determined using experimental density and refractive index measurements. Spectroscopic analyses, such as optical absorption, infrared (IR), and electron paramagnetic resonance (EPR) studies, revealed that the highest redox ratio (Fe²⁺/Fe³⁺) occurs at a Fe₂O₃ concentration of approximately 1.5&#xa0;mol%. At higher Fe₂O₃ levels, Fe³⁺ ions dominate, occupying substitutional sites and increasing glass network rigidity. Dielectric properties, including alternating-current (AC) conductivity (<i>σ</i>_AC), dielectric constant (<i>ε</i>′), dielectric loss (tan <i>δ</i>), and dielectric breakdown strength, were analyzed across various frequencies and temperatures. AC conductivity reached its peak at 1.5&#xa0;mol% Fe₂O₃, while dipole conductivity exhibited the lowest activation energy, suggesting charge transport via polaronic hopping between Fe²⁺ and Fe³⁺ ions. The quantum mechanical tunneling model explains low-temperature AC conductivity, which is influenced by divalent iron ions modifying dielectric behavior. As Fe₂O₃ concentration increases, glass rigidity enhances, reducing dielectric parameters. Overall, Fe₂O₃ primarily integrates into the glass network at octahedral sites, acting as a reducing agent at concentrations ≤ 1.5&#xa0;mol%.</p>