By introducing the amine group into phosphorus extractant, a novel aminophosphine compound bis(2-ethylhexyl) ((2-ethylhexylamino)methyl) phosphine oxide (DEHAPO, abbreviated as A) was synthesized for the extraction of cerium (IV) (Ce(IV)) from sulfate medium (H2SO4). The influence factors including extractant concentration, H2SO4 concentration and temperature on the Ce(IV) extraction were investi-gated and discussed. It is found that the extraction ability of Ce(IV), thorium (IV) (Th(IV)) and rare earths (REs(III)) (La, Gd, Yb) decreases in sulphate medium in the following order:Ce(IV)>Th(IV)>REs(III). The extraction process is an exothermic reaction and the thermodynamic parameters were calculated. The extracted complex of Ce(HSO4)2SO4·A in loaded organic solution was identified by the slope methods and further proved by FT-IR spectral analysis. Stripping studies indicate that Ce(IV) can be effectively stripped from the organic phase. The results of separation factors (β) and saturation loading capacity demonstrate that DEHAPO could be used to selectively extract Ce(IV) from sulphate medium with high separation efficiency and good extraction ability.