Piezoelectric sensors have been widely used in wearable electronic devices with improved integration, which is prone to cause electromagnetic interference (EMI) pollution and affects its operation stability. How to design the materials with integrated piezoelectric sensing and EMI shielding performance is of great significance. In this paper, the Fe3O4@PPy/PINF (FPN) composite film was prepared by depositing pyrrole (Py) on the surface of Fe3O4 nanoparticles and combining it with polyimide (PI) nanofibrous membrane via vacuum-assisted suction filtration. In addition, after encapsulation with a highly soluble fluorine-containing polyimide (FPI) resin, a structurally stable FPI-Fe3O4@PPy/PINF (PFPN) composite film was obtained. The prepared PFPN composites show excellent EMI shielding effectiveness (44.58 dB) through the secondary reflection and multiple absorption effects. Remarkably, the value of the absorption coefficient A can reach 0.74, showing outstanding absorption characteristics. In addition, PFPN composite film also shows unexpected piezoelectric properties with high sensitivity of S = 0.8, short response (25 ms) and recovery (45 ms) time. Its piezoelectric output can reach 4.2 V with stable cyclic output property (>15000 times). This kind of composite film with ultra-low reflection characteristics and favorable piezoelectricity presents a wide range of potential applications in the self-powered wearable electronic fields.