The over-reliance on antibiotics and their enormous misuse has led to warnings of a future without effective medicines and so, the need for alternatives to antibiotics has become a must. Non-traditional antibacterial treatment was performed by using an aray of nanocomposites synergised with exposure to electromagnetic waves. In this manuscript, electrospun poly(vinyl alcohol) (PVA) nanofiber mats embedded with silver nanoparticles (Ag NPs) were synthesized. The nanocomposites were characterized by Transmission Electron Microscope (TEM), Scanning Electron Microscope (SEM), Current-Voltage (I-V) curves, and Thermogravimetric analysis (TGA) along with analysis of antibacterial impact against E. coli and S. aureus bacteria, studied by bacterial growing analysis, growth kinetics, and cellular cytotoxicity. The results indicated a spherical grain shape of silver of average size 20 nm and nanofibers’ mean diameter of less than 100 nm. The nanocomposite mats showed good exposure to bacteria and the ability to sustain release of silver for a relatively long time. Moreover, the applied electromagnetic waves (EMWs) were shown to be a synergistic co-factor in killing bacteria even at low concentrations of Ag NPs. This caused pronounced alterations of the bacterial preserved packing of the cell membrane. Thereby, the treatment with nanocomposite mats under EM wave exposure elucidated maximum inhibition for both bacterial strains. It was concluded that the functioning of nanofiber with silver nanoparticles and exposure to electromagnetic waves improved the antibacterial impact compared to each one alone.