Adsorption of polymers on mineral surfaces allowing colloidal stability have widespread applications in industrial processes. The binding mechanism has been quite well described on oxide surfaces. Mainly in terms of hydrogen bonds and electrostatic interactions between charged sites and polymer segments. This phenomenon has been modelized and the influence of pH. lonic strentgh, and molecular weight can be calculated or predicted. In the case of sparingly soluble substrates such as BaSO4, CaCO3 or CaSO4, several problems arise: the difficulty for the identification of surface sites and the interference of ions coming from the material＇s solubility. In the case of calcite, the solubility imposes dissolved calcium ions in solution which could complex the polyelectrolyte and reduce its solubility. For that purpose, we have measured the binding energy using microcalorimetry. Microcalorimetric measurements have shown that the adsorption enthalpy is weakly endothermic: about + 2 kj/mol. Interestingly, this value is very closed to that of calcium complexation with PANa. It is suggested that the driving force for adsorption is the net gain in entropy of the system. The microcalorimetric adsorption isotherm does not show any evidence for a strongly exothermic interaction between positive edges and negative segment of the polyion. Practically, in most cases, adsorption of polymers is calculated from the decrease of its concentration in the solution after separation of the solid by centrifugation. This procedure does not discriminate therefore between real adsorption and phase separation. To answer the question, we have performed adsorption experiments using a dialysis membrane to separate the solid particles from the solution. It has been established that in some circumstances, depending on the relative amount of calcite, calcium ions and polyelectrolyte, precipitation takes place rather than adsorption. This is especially the case at low polymer concentration (less than 2 g/l). Adsorption isotherms were correctly reproduced, taking into account all solution equilibria, including calcium and sodium binding constants and a solubility limit for the calcium polymer complex: the latter was determined by turbidimetric titration for various polymer molecular weights. Our conclusion is that in the presence of divalent ions which is often the case with sparingly soluble minerals, the surface binding of the polyelectrolyte results from a precipitation rather than an adsorption phenomenon.