Isopiestic molalities of aqueous solutions of phosphoric acid have been measured at 383.15 to 523.15 K. NaCl(aq) served as the isopiestic standard for the calculation of osmotic coefficients. The ion-interaction model gave an excellent fit to the experimental osmotic coefficients by treating H3PO4(aq) as a 1–1 weak electrolyte. Activity coefficients, both real and stoichiometric, were also obtained from the analysis of the isopiestic results. As expected, the ionization of H3PO4(aq) decreased with increasing temperature. However, at higher molalities, the ionization increased with increasing molality (reionization).