Personalized wound dressings with on-site deposition, exudate suction, and reproducible sterilization are urged for treating diabetic wounds. Herein, we have developed nanofiber membranes incorporating a V-shaped photosensitizer (VPS), a donor-acceptor-donor type organic semiconductor with indacenodithienothiophene (IDTT) as the electron-donor and triphenyleno[1,2-c:7,8-c′]bis([1,2,5] -thiadiazole) (TPTz) as the electron-acceptor, for multifunctional wound dressing. The VPS-incorporated nanofiber membranes are in situ deposited on rough wounds by using a handheld electrospinning device, which offers full coverage and better affinity than gauze to stop bleeding and suck exudate rapidly. They are breathable, waterproof, and have bacteria repelling capacity due to their hydrophobicity and negative charges. Upon light irradiation, the VPS in nanofibers undergoes low aggregation-caused quenching and retains high fluorescence and reproducible photodynamic sterilization towards both Gram-positive and Gram-negative bacteria. The nanofiber dressing also promotes cell adhesion and proliferation and exhibits high security in blood biochemistry and hematology. With the above merits, the nanofiber membranes greatly reduce the expression of tumor necrosis factor α and interleukin 6 in serum and wound tissues, expediting the wound healing process. These wound dressings combine the benefits of in situ electrospinning, fiber membrane, and VPS, and will provide strategies for emergency medical operations.