Cationic flotation is one of the most widely accepted technologies for upgrading siliceous iron ore using polysaccharides (mainly starches) as depressing agents for iron bearing minerals while floating silica with amines. In this paper, a group of starches are investigated as depressants for haematite. These starches are wheat, corn, rice, potato and dextrin. The role of starch type on the selectivity of the separation process has been studied through zeta potential, adsorption measurements as well as flotation tests. The effects of type of starch and pH of the medium have been studied. The results indicate that the selectivity of the separation process is strongly affected by the type of starch used, where better results are obtained with corn starch or wheat starch in comparison to the other types. Fourier transform infrared spectroscopy measurements indicated that the interaction between starches and haematite surface is intermolecular interaction.