Abstract An electrospinning method was used to fabricate chitin nanofibous matrix for wound dressings. Chitin was depolymerized by gamma irradiation to improve its solubility. The electrospinning of chitin was performed with 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) as a spinning solvent. Morphology of as-spun and deacetylated chitin (chitosan) nanofibers was investigated by scanning electron microscopy. Although as-spun chitin nanofibers had the broad fiber diameter distribution, most of the fiber diameters are less than 100 nm. From the image analysis, they had an average diameter of 110 nm and their diameters ranged from 40 to 640 nm. For deacetylation, as-spun chitin nanofibous matrix was chemically treated with a 40% aqueous NaOH solution at 60 or 100 °C. With the deacetylation for 150 min at 100 °C or for 1day at 60 °C, chitin matrix was transformed into chitosan matrix with degree of deacetylation (DD) ∼85% without dimensional change (shrinkage). This structural transformation from chitin to chitosan was confirmed by FT-IR and WAXD.