Australia is the largest exporter of iron ore in the world. The high Al content in Australian hematite/goethite ores is detrimental to blast furnace and sinter plant operations. Of the Al containing minerals in iron ore, kaolinite is a common gangue mineral frequently found in iron ore deposits. In iron ore flotation pulp, various ions exist and may inter- fere with the flotation performance when their concentration is high enough. In this work, the role of a water struc- ture-making ion, i.e. Na + , and a water structure-breaking ion, i.e. K + , in the flotation of kaolinite under reverse cationic flo- tation conditions, the most widely used flotation route of iron ore in the world, was studied in a series of laboratory batch flotation tests. It was found that K + , a water structure breaker, can better reduce the zeta potential of kaolinite and thus causes higher flotation recovery of the clay mineral, in comparison to Na + , a water structure maker. The different effects of the alkali metal cations on kaolinite flotation are attributed to the different aggregation degree of kaolinite particles in the presence of these cations.