In this research, the thermodynamic properties of (KCl + N,N-dimethylformamide + water) system were determined based on potentiometric technique. The electromotive force measurements were carried out by using self-made electrodes on the galvanic cell of type Ag vertical bar AgCl vertical bar KCl (m), N,N-dimethylformamide (w), and H2O (1 w)vertical bar K-ISE in various mass fractions of N,N-dimethylformamide in water (0, 0.10, 0.20, and 0.30) in the molality ranging from 0.0094 to 2.5200 mol.kg(-1) at T = (298.2 and 308.2) K and P = 0.1 MPa. Thermodynamic properties modeling was implemented using the DebyeHuckel extended equation, Pitzer ion interaction, and PitzerSimonsonClegg models. Subsequently, unknown parameters for each model were determined and utilized to calculate the thermodynamic properties such as the mean activity coefficients, the osmotic coefficients, the excess Gibbs free energy, and the solvent activity for the system under investigation.