The treatment of chronic diabetic wounds is a major challenge due to oxidative stress, persistent hyperglycemia, and susceptibility to bacterial infection. In this study, multifunctional sandwich‐structured nanofiber dressings (SNDs) are prepared via electrospinning. The SNDs consisted of an outer layer of hydrophobic polylactic acid (PLA) fibers encapsulating MgB2 nanosheets (MgB2 NSs), a middle layer of PLA and polyvinylpyrrolidone (PVP) fibers encapsulating the MgB2 NSs and metformin hydrochloride complex (MgB2‐Met), and an inner layer of water‐soluble PVP fibers encapsulating MgB2‐Met. Because of their special sandwich structure, SNDs have high photothermal conversion efficiency (24.13%) and photothermal cycle performance. SNDs also exhibit a photothermal effect, bacteria‐targeting effect of MgB2, electrostatic attraction ability of metformin hydrochloride (Met), and strong antibacterial activity against Escherichia coli (E. coli) and methicillin‐resistant Staphylococcus aureus (MRSA). SNDs can eliminate intracellular reactive oxygen species (ROS) by regulating the hydrogen release from MgB2. In addition, SNDs have good biocompatibility, can effectively inhibit the inflammatory factor Interleukin‐6 (IL‐6), and promote granulation tissue formation, collagen deposition, and diabetic wound healing. These findings offer a promising approach for clinical treatment of diabetic wounds.