Flotation separation and recovery of rare earth minerals (REM) have returned to an important position due to the growing strategy demand for rare earth elements (REE).In this paper,a comparative inves-tigation into the floatability of bastnaesite ((Ce,La)FCO3) was conducted by using three di/trialkyl phosphate collectors,di(2-ethylhexyl) phosphate (DEHPA),dibutyl phosphate (DBP) and tributyl phos-phate (TBP).The density functional theory (DFT) computation recommends that the chemical activity of the three phosphate collectors is in order of DEHPA ≥ DBP ＞＞ TBP,and their hydrophobization as-suggested by the lgP (oil-water partition coefficient) value is in the order of DEHPA ＞ TBP ＞ DBP.The micro-flotation indicates that the preferable pH values for flotation of bastnaesite with the three phosphate collectors are 7.0-8.0,and DEHPA achieves much higher flotation recovery of bastnaesite,followed by DBP,and then TBP,which coincides with their reactivity and hydrophobicity,the two pre-requisites for froth flotation.The contact angle,zeta potential,Fourier transform infrared spectroscopy(FTIR) and X-ray photoelectron spectroscopy (XPS) deduce that DEHPA likely reacts with the Ce(Ⅲ)atoms of bastnaesite interface through its O atom(s) of the P(O)-O group to generate the Ce-O-P bonds,and its two 2-ethylhexyl groups orient outside for attaching bubbles,resulting in flotation enrichment of bastnaesite.Furthermore,this investigation offers a novel strategy for developing col-lectors in selective beneficiation of REM.