Extraction-precipitation is a new type of separation technology. By forming a solid extracting complex in the aqueous phase, the process can realize efficient recovery of rare-earth elements (REEs). Compared with the traditional liquid−liquid extraction and chemical precipitation, its advantage lies in that no organic solvent is used and the extraction-precipitant can be recycled. In this study, two novel extractionprecipitants of 2,2′-((cyclohexane-1,1-diylbis(4,1-phenylene))bis(oxy)) diacetic acid (CPDA) and 2,2′-((oxybis(4,1-phenylene))bis(oxy)) diacetic acid (OPDA) were developed and compared with the REE recovery performance of the other extractionprecipitants, i.e., 2,2′-((propane-2,2-diylbis(4,1-phenylene))bis(oxy)) diacetic acid (PPDA) and 2-(4-(2,4,4-trimethylpentan-2-yl) phenoxy) acetic acid (POAA). The effects of aqueous phase pH value, reaction equilibrium time, saponification degree, extraction-precipitant amount, and the ratio of REE were investigated. The mechanism for the extraction-precipitation process was indicated to be cation exchange. CPDA, OPDA, and PPDA with a dicarboxylic acid structure showed stronger loading capacities and faster precipitation speed for neodymium (Nd) than POAA with a monocarboxylic acid structure. Among these extraction-precipitants, CPDA had the lowest water solubility and therefore could be easily recycled. The extraction-precipitation technology was successfully used to recover REE from the lotion of waste neodymium ferroboron (abbreviated as NdFeB) magnets with a recovery rate of 90%. The concentration of REE was increased from 51.4 mg/L to 19.6 g/L, accordingly, and the enrichment was about 400 times. This study provides new insight into the recycling of REE secondary resources.