The kaolinite presence in bauxite ores increases caustic soda consumption during the digestion step in the Bayer process. Depending on the kaolinite content, the utilization of the ore in the Bayer process may be unfeasible. This investigation addressed the variables involved in kaolinite flotation through microflotation experiments in a Hallimond tube and zeta potential determinations. The tests were performed with a pure sample of kaolinite (96%). Five collectors were tested: Duomeen T (DT), cetyl pyridinium chloride (CPC), cetyltrimethylammonium bromide (CTAB), dodecylamine (DDA) and Flotigam EDA (EDA). Four of them performed well as collectors, at a concentration of 1×10−4 mol/L: CPC, CTAB, DDA and EDA. The kaolinite isoelectric point (IEP) was determined at pH = 4.6. The IEP was shifted towards higher pH values in the collectors’ presence, indicating specific adsorption onto the mineral surface.