Cadmium is a harmful pollutant in soil. Here, an aminated polyacrylonitrile (PAN) nanofiber membrane is obtained by electrospinning and amination modification for effective in situ remediation of bivalent cadmium (Cd(II)) contaminated kaolin. The aminated PAN (APAN) nanofiber membrane has the potential to be used as permeable reactive barrier (PRB) combined with electrokinetics (EK) for the remediation of potentially toxic metal contaminated soil. Morphology and chemical characterizations of the nanofibers are analyzed by scanning electron microscopy and attenuated total reflectance Fourier transform infrared spectroscopy. The maximal adsorption capacities of Cd(II) on APAN nanofiber membrane, as calculated from the Langmuir model, are 51.8 mg g−1. In addition, the obtained APAN nanofiber membrane can also be facilely regenerated through the adsorption/desorption experiments (5 cycles). The APAN‐15 nanofiber membrane is used for the remediation of Cd(II) contaminated kaolin. The pH, water content, conductivity, and Cd(II) concentration of kaolin are detected after EK process. These results show that the APAN‐15 nanofiber membrane works as adsorption medium and can accelerate the migration rate of Cd(II) in kaolin, stabilize the pH, and water content. The APAN nanofiber membrane as PRB material can remove Cd(II) in soil effectively and remediate the soil via the EK/APAN process.