The current work intends to reveal molecular insights into the extraction of aromatic and polyaromatic components utilizing deep eutectic solvents (DESs). The atomic-level classical molecular dynamics (MD) simulation approach is then applied to explore the equilibrium phase behaviors of the DESs + solute + solvent ternary system with regard to solvent-rich and raffinate-rich phases. To investigate the influence of feed concentration, different concentrations were selected from the stated experimental runs, which yielded good selectivity and distribution coefficient values. The nonbonded interaction energies of various species and the structural features such as radial distribution functions, spatial distribution functions, combined distribution functions, and the average number of hydrogen bonds are then calculated. To verify the MD simulation approach, the concentration in both the phases was compared with the liquid–liquid equilibria experimental data. In the concluding section, the extraction of an aromatic drug, namely, nitenpyram, from an aqueous phase, is explored with short- and long-range interaction.