This work highlights the enrichment of Nd(III) via hollow fiber supported liquid membrane (HFSLM). In terms of the practicability to separate Nd(III), the influence of significant factors and the behavior of different carrier concentrations were evaluated. Using Di-(2-ethylhexyl)phosphoric acid (D2EHPA) as a ligand carrier, high enrichment performance of Nd(III) can be achieved. Under optimum conditions, extraction and stripping of Nd(III) reached 99.80% and 78.58%, respectively. Further, the active Nd(III) transportation was analyzed to emphasize key parameters that govern the separation process. The values kex (cm/s) and Δex (%) were found to be 1.38×10-5 and 81.20, respectively, indicating the mass transfer due to chemical reaction is the controlling step. Density-functional theory (DFT) was applied to explore the interaction mechanisms from a microscopic viewpoint. Comprehensive analysis was made to achieve better insight regarding the reaction mechanisms and the structural chemistry underlying the process of Nd(III) enrichment.