Due to the rapid development of information technology and the trend toward miniaturization of electronic equipment, the research on electromagnetic interference (EMI) shielding materials is rapidly moving toward low-dimensional, core−shell, and lightweight directions, with a wide range of application prospects in various fields. In this study, using pDA as a binder, poly(vinylidene difluoride) (PVDF)/Fe 3 O 4 @pDA@Ag nanofiber membranes (NFMs) with a multicore−shell structure were prepared by in situ growth of Ag nanoparticle (NP) layers on the fiber surface of electrospun PVDF/Fe 3 O 4 NFMs fabricated in batch. Compared to PVDF@pDA@Ag NFM, the average EMI shielding efficiency (SE) of PVDF/Fe 3 O 4 @pDA@Ag NFM reached 82.31 dB because of the increased hysteresis and multireflection losses inside the NFM caused by the moderate addition of Fe 3 O 4 NPs. In addition, the synergistic effect of Fe 3 O 4 and Ag NPs increased the microwave attenuation and impedance matching of composite NFM, further enhancing its EMI SE.