There are still challenges in the recovery of rare earth elements (REEs) from leaching liquor of ion-adsorption type rare earth ore. In this paper, unsaponified N, N-di(2-ethylhexyl)-diglycolamic acid (HDEHDGA) was used to develop a green extraction process for efficient separation and enrichment of REEs. The cation exchange mechanism of RE(III) extraction was proposed by slope analysis and FT-IR spectra. HDEHDGA exhibited excellent extraction performances, such as short equilibrium time, high selectivity towards RE(III) and easy stripping by 0.5 mol/L HCl solution. REEs was enriched from 287.5 mg/L to 63.30 g/L by five-stage counter-current extraction and three-stage counter-current stripping using unsaponified HDEHDGA. The enrichment factor reached 220, and the proportion of REEs was increased from 80.76 wt% to 98.82 %. The loss of REEs was controlled below 2.14 wt%. This extraction strategy helps to improve the REEs recovery and avoid ammonia–nitrogen wastewater, which demonstrates its application potential in the ion-adsorption type rare earth ore.