The electrokinetic properties and flotation behaviour of Israeli francolite and calcite were studied in order to develop a process for direct flotation of the Negev phosphates. The surface charges of the minerals were measured by microelectrophoresis at different pH values in the presence of the collector. The results suggest that the collector is adsorbed predominantly on the negatively charged surface of the francolite at pH range 7 to 9. The flotation behaviour of francolite and calcite was studied with several amine collectors in single mineral systems and mixtures. The flotation recovery curves agree with the electrokinetic studies; a primary amine was found to be a very effective collector for francolite. A Denver flotation test with Arad phosphate using the primary amine collector resulted in high-grade marketable phosphate concentrates.