Flexibility, protection against harmful electromagnetic (EM) waves, and mimicking movement patterns of human beings are among the most required features of advanced textiles. In this regard, the present study was conducted to investigate the possibility of producing flexible, piezoelectric, and EM-sensitive multifunctional nanofibers. Porous core-shell Fe3O4@MnO(2)Nanoparticles (NPs) were synthesized and dispersed in poly (vinylidene fluoride) through solution mixing methods in different concentrations. Then, nanofibers were prepared by the electrospinning technique. Extensive characterizations including morphological, structural, piezoelectric response, and EM wave absorbance tests were performed on both synthesized NPs and electrospun mats. The effects of filler content, piezoelectric dimension, and test dynamic condition on the output voltage of the piezoelectric generator were also assessed. FTIR and XRD investigations respectively showed that the beta phase content increased up to 10% and 7% in presence of 4% NPs that led to an increase of up to 105% in piezoelectric response (up to 23.5 V). Output voltages increased linearly with slopes of 2.83, 1.92, 0.55, 0.306, and 0.086 by increasing the NP content, frequency, piezoelectric area, force, and thickness, respectively. The results of the study indicated that produced nanofibers can absorb significant EM waves in addition to showing high piezoelectric response.