The electrical conductivity (Κ), molar conductivity (Λm), and limiting molar conductivity (Λmo) of NaCl and KCl in different compositions of aqueous PVOH and PAAM (0.1%, 0.5%, and 1.0% w/v considering the solubility of PVOH and PAAM in water) were determined at temperatures from 298 to 318 K with a difference of 5 K. The concentration of NaCl and KCl was from 2.0 to 10.0 × 10−3 mol.dm−3. The electrical conductivity of KCl was higher than NaCl. The electrical conductivity increased with the increase in concentration of NaCl and KCl, while a reverse trend was observed for the molar conductivity. The electrical conductivity and molar conductivity increased with the increase of temperature and concentration of polymer in the solvent. The change in conductive properties of NaCl and KCl in aqueous PVOH and PAAM was used to evaluate the fundamental changes inside the solution at the molecular level. The degree of dissociation and dissociation constant decreased with the increase of temperature due to the exothermic nature of the dissociation of NaCl and KCl. The ion-ion and ion-solvent interactions were evaluated by the Debye-Huckel relation. The ion-ion interaction (A) decreased, while the ion-solvent interaction (B) increased with the increase of temperature. The thermodynamic parameters for the dissociation of NaCl and KCl were also determined to understand the energetics and spontaneity of the process. The results are explained in terms of electrostatic interactions, structural effects, and energetics of the processes involved.