The behaviour of cationic amine collectors used in the reverse cationic flotation of quartz from iron oxide minerals appears to change from one mineral system to the other, deviating from theoretical predictions based on the reagent chemistry. The performance of five amine collectors in the flotation of a South African iron ore and a Brazilian iron ore, each with different textural characteristics was investigated using reverse flotation techniques from Brazil. Furthermore, the overall collection efficacy of the five collectors in iron ore reverse flotation was analysed. Batch flotation tests and a mineralogical characterisation of the ore using QEMSCAN was conducted. Mineral liberation heavily influenced the flotation behaviour of the two ores. A well liberated Brazilian iron ore was amenable to reverse cationic flotation, whereas, the texturally complex South African iron ore did not respond well to reverse cationic flotation. Alkyl ether amines proved to be superior to quaternary amine compounds in the flotation of quartz from hematite.