Since 1980′s natural polymers are studied as sources for solid polymer electrolytes (SPEs) in opto-electronic equipment because of their abundance in the environment, inexpensiveness, and biological degradation characteristics. Xanthan gum is a naturally occurring polysaccharide found in the microbial world, and its main advantage is to produce transparent solutions with elevated viscosity and stability including wide range of temperature. Therefore, the present paper presents the FTIR and impedance study of xanthan gum as a host matrix for the ionically conducting membranes. Different contents of proton conducting species were incorporated into the polymer host and the membranes were realized by the method of solution casting. The FTIR results indicated that the electrolytes were formed by the polymeric network. The frequency independent conductivity response pointed the best dc conductivity values of 7.26 × 10−5 to 3.92 × 10−4 S cm−1, in the temperature range from 20 to 80 °C, for the sample with 2.00 g of acetic acid. The occurrence of the electrode polarization was interpreted by the combination of the complex dielectric permittivity (ε*), loss tangent (tan δ), conductivity (σ), and complex electric modulus (M*).