Nanofibrous scaffolds offer significant promise for wound healing due to their ability to absorb exudates, prevent microbial contamination, and enhance oxygen diffusion. However, challenges remain in fully realizing their clinical potential, as previous research has primarily focused on scaffolds made of two polymers or those encapsulating therapeutic agents within nanofibers. Additionally, scaling up fabrication while maintaining functionality presents a significant challenge. This study introduces a novel type of nanofibrous scaffold, combining poly (ethylene oxide) (PEO), poly (caprolactone) (PCL), and chitosan (CS) in various mass ratios, electrospun using Nanospider™ technology. The scaffolds featured fiber diameters ranging from 134 ± 37 to 148 ± 38 nm and exhibit high gram-per-square-meter values between 6.8 and 8.6 g/m2. An optimal balance of hydrophilicity was achieved, and the scaffolds demonstrated superior breathability with moisture vapor transmission rates ranging from 1904.3 ± 28.6 to 2005.7 ± 42.9 g/m2/day, outperforming commercial wound dressings. Additionally, a wide range of hydrolytic degradation rates (3.8 ± 1% to 73.2 ± 0.8%), elongation at fracture (21% to 0.8%), and Young’s modulus (106.7 ± 8.5 MPa to 170.7 ± 11.9 MPa) were observed. Surface-immobilized tetracycline (TET) significantly enhanced antibacterial efficacy, with inhibition zones exceeding 20 mm against Escherichia coli. Our findings confirm that scaffold properties can be effectively tailored by adjusting the PEO/PCL ratio, advancing customization for wound care. Post-fabrication soaking in TET solutions further boosts antibacterial performance and allows for tailored post-production adjustments. Compared to existing studies, this approach simplifies customization and improves the practicality of wound care solutions.