A new ferrofluid extractant (Fe3O4 @SiO2-WDES) was ingeniously prepared by coating magnetic Fe3O4 @SiO2 microspheres with water-based deep eutectic solvent (WDES) and used for dispersive liquid-liquid microextraction (DLLME) and HPLC determination of naphthalene-derived plant growth regulators (PGRs, i.e., 1-naphthylacetic acid, 2-naphthylacetic acid, 1-naphthoxy acetic acid, 2-naphthyloxyacetic acid and 1-naphthylacetamide) in edible oil. Herein, mass transfer of the analytes in DLLME was significantly enhanced via increasing the contact surface by employing the microspheres as the supporter and dispersant of WDES, and phase separation can be efficiently achieved using an external magnet rather than centrifugation in traditional DLLME. Response surface methodology (RSM) based on Box-Behnken design (BBD) was employed for the optimization of core experimental conditions, and Analytical Eco-Scale and Analytical GREEnness Metric Approaches were adopted to evaluate the degree of greenness of the procedure. Under the optimal conditions, satisfactory performances of linearity ranged from 5 to 100 μg/L (R2 ≥ 0.9982), limit of detection (0.58–0.91 μg/L), limit of quantitation (1.9–3.0 μg/L), precision (RSDs ≤ 5.5%), recovery (81.3%−108.1%) and negligible matrix effect were achieved, which introduced a promising alternative route for the determination of naphthalene-derived plant growth regulators in edible oil.