Excess biological fluids around skin wounds can lead to infections and impede the healing process. Researchers have extensively studied dressings with varying water contents for wound care. However, hydrophilic and hydrophobic-hydrophilic dressings often face challenges such as slow fluid transfer and excessive retention. This study introduces an innovative approach involving the use of superhydrophobic–hydrophobic–hydrophilic dual-gradient electrospun nanofibers to form a 3D biomimetic nanofiber scaffold (3D BNSF). The 3D BNSF is composed of hydrophobic polycaprolactone and thermoplastic polyurethane, along with antibacterial, superhydrophobic nano-chitin particles. In vitro and in vivo experiments have demonstrated that this scaffold exhibits excellent antibacterial properties and compatibility with cells, facilitating complete wound healing and regeneration. This study offers a new perspective on the targeted acceleration of wound healing, with the potential to become an alternative strategy for clinical applications.