Direct disposal of concentrate brines, generated by many industrial sectors, causes serious environmental concerns. An industrial sector that produces high concentrate brines is softening water industry, in particular during the regeneration of ion exchange resins. These brines are mainly rich in sodium, magnesium and calcium chlorides, thus, their regeneration, by removal/recovery of magnesium and calcium, can be a valuable option to turn the brine into a source of minerals and reduce disposal costs and environmental concerns. In this regards, one of the goals of EU-funded ZERO BRINE project is to develop a treatment chain for the valorization and regeneration of spent brines from water softening plants. The treatment chain consists of Nanofiltration, crystalization and evaporation to regenerate spent brines and recover high purity magnesium and calcium hydroxides. In this work, a wide experimental campaign was carried out to recover high purity magnesium and calcium via selective chemical precipitation of relevant hydroxides adding by injection of an alkaline solution in two consecutive steps at controlled pH. Precipitations were performed using synthetic brine solution, mimicking the retentate produced by nanofiltration, some of them were carried out considering a pre-treatment step to remove bicarbonate ions.