Wound healing can be a complex and slow process for the human body, particularly if it is chronic. Photothermal therapy (PTT) and photodynamic therapy (PDT) can be used to accelerate wound healing. As opposed to current PDT studies using well‐known photosensitizers, this work use novel polyvinyl alcohol (PVA) and melanin nanoparticles (MNPs) containing hybrid nanofibers prepared by electrospinning techniques to enhance wound healing with/without UV light. Blend and core‐sheath nozzles are utilized to obtain sustainable and biocompatible MNP‐PVA blend, and core‐sheath hybrid nanofibers and 30, 60, and 300 s of UV‐A irradiation are tested in terms of photoinactivation efficiencies for Escherichia coli (E. coli). The MNP‐PVA blend with a diameter of 324 nm and the core‐sheath nanofibers with a diameter of 468 nm both showed killing effect on E. coli about 41.6% and 32%, respectively, under 30 s of UV‐A irradiation. Increased irradiation time activates the protective effect of MNPs located in nanofibers, thereby decreasing photoinactivation efficiency. Moreover, the MNP‐PVA core‐sheath nanofibers with 30 s of UV‐A irradiation promote the closure of wound to 99.2% at 24 h.