The solubility of thorium under oxide and/or hydroxide forms has been extensively studied for many years. Nevertheless, a large discrepancy in the solubility values is noticed in the literature. We study Th atom exchange between thorium oxide surfaces and various aqueous solutions (0.01 mol*L−1 NaCl for 0.0 < pH < 5.2) to address this issue. By solid-state characterization [X-ray photoelectron spectroscopy (XPS), scanning electron microscopy, and atomic force microscopy], we determined that 80% of the XPS accessible near the surface region of sintered thorium oxide is represented by the less reactive ThO2(cr) grains. The remaining 20% corresponds to ThOx(OH)y(H2O)z, which is largely associated with grain boundaries. Only the latter fraction is involved in solid/solution exchange mechanisms. Local conditions (thorium concentrations, pH values, etc.) in grain boundaries lead to an adjustment of the "local solubility constraints" and explain the thorium concentration measured in our experiments. For pH <5.2, the thorium concentration and pH gradient between the bulk solution and grain-boundary regions imply that the solubility values mainly depend on the availability and accessibility of ThOx(OH)y(H2O)z. We have performed two solubility experiments with a 232ThO2(cr) solid in a 0.01 mol*L−1 NaCl solution for 300 days. In a first experiment, we measured 232Th concentrations in dissolution experiments in order to determine the detachment rates of Th atoms from the solid surface. In a subsequent step, we added 229Th to the solution in order to measure the surface attachment rate for dissolved Th atoms. This allowed an assessment of the net balance of Th atom exchange at the solid/solution interface. The empirical solubility data do not correspond to the thermodynamic bulk phase/solution equilibrium because measured solution concentrations are controlled by site-specific exchange mechanisms at the solid/solution interface. Therefore, for sparingly soluble solids, one needs to quantify site-specific surface attachment and detachment rates if one wants to assess solubility constraints.