Abstract: The properties of metal sites on the surface of ilmenite and olivine are highly similar and are considered difficult to separate. A new ternary combined collector (ABN) was assembled using aluminum trichloride (Al), benzohydroxamic acid (BHA), and sodium oleate (NaOL) for the flotation separation of ilmenite and olivine. Single mineral flotation experiments showed that ilmenite was recovered at 90.4% and olivine at 25.9% under the condition of pH = 8 and a molar ratio of Al, BHA, and NaOL at 2∶3∶1. In comparison with the BHA system, the recovery rate of ilmenite was increased by 58.17%. Surface Zeta potential measurement and XPS analysis revealed that the chemical adsorption of ABN at Ti (OH) and Fe (OH) sites resulted in a positive shift of the surface potential by 47.32 mV, with only a small amount of electrical adsorption on the surface of olivine. The results of powder contact angle measurement indicated that ABN increased the surface contact angle difference between ilmenite and olivine from 1.01° to 20.41°. The selective adsorption of ABN on the surface of ilmenite led to an increased wettability difference between ilmenite and olivine, thereby facilitating the flotation separation of the two minerals.