The objective of this investigation was to develop a new class of antibacterial material in the form of nanofibers coated with silver nanoparticles (AgNPs) using a modified coaxial electrospinning approach. Through manipulation of the distribution on the surface of nanofibers, the antibacterial effect of Ag can be improved substantially. Using polyacrylonitrile (PAN) as the filament-forming polymer matrix, an electrospinnable PAN solution was prepared as the core fluid. A silver nitrate (AgNO₃) solution was exploited as sheath fluid to carry out the modified coaxial electrospinning process under varied sheath-to-core flow rate ratios. Scanning electron microscopy and transmission electron microscopy demonstrated that the sheath AgNO₃ solution can take a role in reducing the nanofibers' diameters significantly, a sheath-to-core flow rate ratio of 0.1 and 0.2 resulting in PAN nanofibers with diameters of 380 ± 110 nm and 230 ± 70 nm respectively. AgNPs are well distributed on the surface of PAN nanofibers. The antibacterial experiments demonstrated that these nanofibers show strong antimicrobial activities against Bacillus subtilis Wb800, and Escherichia coli dh5α. Coaxial electrospinning with AgNO₃ solution as sheath fluid not only facilitates the electrospinning process, providing nanofibers with reduced diameters, but also allows functionalization of the nanofibers through coating with functional ingredients, effectively ensuring that the active antibacterial component is on the surface of the material, which leads to enhanced activity. We report an example of the systematic design, preparation, and application of a novel type of antibacterial material coated with AgNPs via a modified coaxial electrospinning methodology.