In this paper, a novel collector, 2-ethyl-2-hexenoic hydroxamic acid (EHHA) was prepared and characterized by elemental analysis, infrared, H-1 NMR, C-13 NMR and mass spectra. The flotation performance and adsorption mechanism of EHHA to ilmenite were investigated by micro-flotation tests, density functional theory (DFT) calculations, FTIR spectra, zeta potential and solution chemistry analyses. The microflotation results indicated that EHHA exhibited superior flotation performance compared to isooctyl hydroximic acid (IOHA) and octyl hydroxamic acid (OHA), and floated out 84.03% ilmenite at pH 8.0 with 250 mg/L dosage. The analyses of FTIR spectra and zeta potential demonstrated that EHHA might chemisorb onto ilmenite surfaces by form of five-membered chelates. The solution chemistry analyses further inferred that at pH 6.3-10.5, both Fe and Ti species on ilmenite surfaces could chelate EHHA. DFT calculation results implied EHHA owned the strongest affinity to ilmenite among the three C8 hydroximic acids. To discern the sharply improving floatability of ilmenite at pH 8-10, a schematic alpha-adsorption molecule-ion model of EHHA on ilmenite surfaces was suggested. (C) 2015 Elsevier B.V. All rights reserved.