1,10-phenanthroline (Phen) was introduced as the novel collector for the selective separation of ilmenite from titanaugite. Micro-flotation showed that Phen was a more effective collector for ilmenite flotation from pH 2 to 12 compared with benzohydroxamic acid (BHA), and the maximum increase in ilmenite recovery (~20%) was observed at pH 6. Titanaugite kept at very low level of floatability (recovery < 5%) during micro-flotation test. FTIR and XPS analyses indicated that Phen and BHA adsorbed onto ilmenite surface via chemisorption and the interaction between Phen and ilmenite was intenser than that of BHA. XPS results also showed that Phen reacted with both iron (ferrous and ferric) and titanium on the ilmenite surface. A five membered ring structure appeared to form during the adsorption of Phen onto the ilmenite surface.