Polylactic acid (PLA) is a biodegradable polymer made from natural sources, and its electrospinning (e-spinning) nanofiber membrane doped with antibacterial ingredients is widely used in the field of medical dressings. In this research, 9 wt% of rosmarinic acid (RosA) and 0.04 wt% of graphite oxide (GO) with synergistic antibacterial activity were introduced into the e-spinning PLA precursor solution, and the obtained PLA nanofiber membrane showed good antibacterial properties and wound healing effects. At the same time, a nonionic amphiphilic polymer, polyethylene glycol (PEG), was also introduced into this system to improve the hydrophilicity of the e-spinning membrane for wound healing application. The morphological characterization showed the RosA/GO and PEG did not affect the e-spinning of PLA. The tests of mechanical performance and wettability demonstrated that PEG and RosA/GO incorporated in PLA have migrated easily to the surface of the fiber. The e-spun PLA/PEG/RosA/GO membrane showed good antibacterial activity and promoted initial wound healing quickly, which would be a promising application in wound dressing.