Lithium, a rare-earth element, has been in increasing demand. Spodumene flotation is an important and challenging step for lithium extraction and production from lithium ore. In the present work, flotation tests for three pure minerals (i.e., spodumene, quartz and feldspar) and a real spodumene ore were carried out at laboratory scale. The results showed that YOA, a mixture of oleic acid and dodecylamine with the molar ration of 10:1, could be used as collector to produce a spodumene concentrate with grade of 5.59% Li₂O from the feed ore with grade of 1.48% Li₂O where 85.24% of Li₂O was recovered to the concentrate. The measured zeta potential, contact angle and adsorption capacity indicated that YOA was preferentially adsorbed on spodumene instead of on quartz or feldspar, with the spodumene surface being more hydrophobic than that of feldspar or quartz. The adsorption energies of YOA on spodumene were calculated and the results provided insights into the superior flotation performance obtained in the present work.