Nano zero-valent iron (NZVI) is widely used for reducing chlorinated organic pollutants in water. However, the stability of the particles will affect the removal rate of the contaminant. In order to enhance the stability of nano zero-valent iron (NZVI), the particles were modified with F-127 as an environmentally friendly organic stabilizer. The study investigated the effect of the F-127 mass ratio on the colloidal stability of NZVI. Results show that the sedimentation behavior of F-NZVI varied at different mass ratios. A biphasic model was used to describe the two time-dependent settling processes (rapid sedimentation followed by slower settling), and the settling rates were calculated. The surface morphology of the synthesized F-NZVI was observed with a scanning electron microscope (SEM), and the functional groups of the samples were analyzed with Fourier Transform Infrared Spectroscopy (FTIR). Results show that the F-127 was successfully coated on the surface of the NZVI, and that significantly improved the stability of NZVI. Finally, in order to optimize the removal rate of 2,4-dichlorophenol (2,4-DCP) by F-NZVI, three variables were tested: the initial concentration 2,4-DCP, the pH, and the F-NZVI dosage. These were evaluated with a Box-Behnken Design (BBD) of response surface methodology (RSM). The experiments were designed by Design Expert software, and the regression model of fitting quadratic model was established. The following optimum removal conditions were determined: pH = 5, 3.5 g·L−1 F-NZVI for 22.5 mg·L−1 of 2,4-DCP.