Salt rejection and ion selectivity of NF-255 and NF-45 nanofiltration (NF) membranes were investigated. The rejection of two cations (Ne+, Ca2+) and two anions (Cl-, SO42-) which are common in natural and in industrial wastewater, were studied as a function of pH at permanent pressure and temperature. The ion rejection of NF membranes were investigated in single salt solutions like NaCl, CaCl2, Na2SO4, CaSO4, and in multicomponent systems that contained all the previous ions. We found that, there is a minimum rejection of the Na+ and Cl- ions between pH 4-5 in NF-255 and between pH 7-8 in NF-45. The rejection of calcium ions were increased in each case at lower pH in both membranes. However the pH value where the ion rejection behaviour of membranes changed, were different: pH 4 in NF-255 and pH 8 in NF-45. In NF-45 the chloride ion has negative rejection which depends on the quality of ions and the pH. We found that below pH values of 4 the selectivity of mono- and multivalent cations considerable increased in NF-255. This phenomena may be used for separation of calcium ions from sodium ions from weakly acidic (hydrochloric and sulfuric acid) solution, e.g. regeneration solution of sodium form softening ion exchangers.