Photo‐electronic devices based on reactive oxygen species (ROS) generation suffer a crucial limitation in wound treatment due to their sandwich structure, which prevents the contact of ROS with wound tissue. In this work, the first anti‐sandwich structured visible‐light/electricity dual‐responsive wound dressing is constructed for treatment of methicillin‐resistant Staphylococcus aureus (MRSA), based on selenoviologen‐appendant polythiophene (SeV2+‐PT)‐containing polyacrylamide hydrogels. The new wound dressing is named an anti‐sandwich structured photo‐electronic wound dressing (PEWD). The unique structure of PEWD enables its use in synergistic electrodynamic and photodynamic therapy (EDT and PDT), providing rapid, on‐demand, and sustained generation of ROS in situ via short‐time light irradiation and/or wireless‐controlled electrification. The PEWD possesses good flexibility, excellent biocompatibility, and fast response, as well as sustained ROS generation in a physiological environment. Animal experiments demonstrate effective ROS generation in 6 s under irradiation and electrification, inhibiting infection at an early stage, and substantially shortening the healing time of bacterial infection (to within 7 days). This proof‐of‐concept research holds great promise in developing new flexible PEWD, and novel strategies to improve wound treatment.