Herein, we report the design of electrospun ultrathin fibers based on polycaprolactone (PCL), polyethylene glycol (PEG), and gelatin methacryloyl (GelMA), and their potential bactericidal activity against three different bacteria Staphylococcus aureus, Pseudomonas aeruginosa, and Methicillin-resistant Staphylococcus aureus (MRSA). We evaluated the morphology, chemical structure and wettability before and after UV photocrosslinking of the produced scaffolds. Results showed that the developed scaffolds presented hydrophilic properties after PEG and GelMA incorporation. Our developed scaffolds were thus able to significantly reduce gram-positive, negative, and MRSA bacteria. Furthermore, we performed a series of study for better mechanistic understanding of the scaffolds bactericidal activity through protein adsorption study and analysis of the reactive oxygen species (ROS) levels. In summary, we have demonstrated the design and generation of electrospun fibers with improved hydrophilicity and efficient bactericidal activity without the association of any antibiotics.