A highly deacetylated (97.5%) chitosan in 50% acetic acid was electrospun at moderate temperatures (25 -70 degrees C) in the presence of a low content of polyethylene oxide (10 wt% PEO) to beadless nanofibers of 60 -80 nm in diameter. A systematic quantitative analysis of the solution properties such as surface tension, conductivity, viscosity and acid concentration was conducted in order to shed light on the electrospinnability of this polysaccharide. Rheological properties of chitosan and PEO solutions were studied in order to explain how PEO improves the electrospinnability of chitosan. Positive charges on the chitosan molecule and its chain stiffness were considered as the main limiting factors for electrospinability of neat chitosan as compared to PEO, since surface tension and viscosity of the respective solutions were similar. Various blends of chitosan and PEO solutions with different component ratios were prepared (for 4 wt% total polymer content). A significant positive deviation from the additivity rule in the zero shear viscosity of chitosan/PEO blends was observed and believed to be a proof for strong hydrogen bonding between chitosan and PEO chains, making their blends electrospinnable. The impact of temperature and blend composition on the morphology and diameter of electrospun fibers was also investigated. Electrospinning at moderate temperatures (40-70 degrees C) helped to obtain beadless nanofibers with higher chitosan content Additionally, it was found that higher chitosan content in the precursor blends led to thinner nanofibers. Increasing chitosan/PEO ratio from 50/50 to 90/10 led to a diameter reduction from 123 to 63 nm. Producing defect free nanofibrous mats from the electrospinning process and with high chitosan content is particularly promising for antibacterial film packaging and filtration applications. (C) 2011 Elsevier Ltd. All rights reserved.