Ionic liquids are the key materials for the recovery of rare earths, which have attracted considerable attentions in the recent years. In this article, a novel ionic liquid [trihexyl(tetradecyl)phosphonium](2)[benzene-1,4-dioxydiacetate] ([P-6,P-6,P-6,P-14](2)[BDOAC]) has been developed for rare earth (RE) recovery. Experiments show that [P-6,P-6,P-6,P-14](2)[BDOAC] can form solid extracting complexes with rare earth ions from aqueous phase. The precipitation process of [P-6,P-6,P-6,P-14](2) [BDOAC] was investigated by IR and single -crystal X-ray diffraction analysis (SC-XRD), respectively. Nd[BDOAC]1 5(H2O)z is given as a proposed structure of the precipitate. The sizes of obtained precipitated particles are larger than those from conventional precipitation methods. Stripping of RE from the precipitate by 0.015 mol/L HCl is effectively achieved. [P-6,P-6,P-6,P-14](2)[BDOAC] can be regenerated in the RE recovery strategy. Because of bifunctional [BDOAC](2)-, the [P-6,P-6,P-6,P-14](2) [BDOAC] reveals better recovery capacity for RE. The recovery of RE from simulated waste NdFeB feed solution using [P-6,P-6,P-6,P-14](2) [BDOAC] was studied. The recovery rate of RE achieves 90.6%, and the purity of RE increases from 44.9% to 98.1%. (C) 2018 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.