Chitosan (CS) aqueous salt blended with polyvinyl alcohol (PVA) nanofibre mats was prepared by electrospinning. CS was dissolved with hydroxybenzotriazole (HOBt), thiamine pyrophosphate (TPP) and ethylenediaminetetraacetic acid (EDTA) in distilled water without the use of toxic or hazardous solvents. The CS aqueous salts were blended with PVA at different weight ratios, and the effect of the solution ratios was investigated. The morphologies and mechanical and swelling properties of the generated fibres were analysed. Indirect cytotoxicity studies indicated that the CS/PVA nanofibre mats were non-toxic to normal human fibroblast cells. The CS-HOBt/PVA and CS-EDTA/PVA nanofibre mats demonstrated satisfactory antibacterial activity against both gram-positive and gram-negative bacteria, and an in vivo wound healing test showed that the CS-EDTA/PVA nanofibre mats performed better than gauze in decreasing acute wound size during the first week after tissue damage. In conclusion, the biodegradable, biocompatible and antibacterial CS-EDTA/PVA nanofibre mats have potential for use as wound dressing materials.