Thermal degradation of as-electrospun chitosan membranes and samples subsequently treated with ethanol and cross-linked with glutaraldehyde has been studied by thermogravimetry (TG) coupled with an infrared spectrometer. The influence of the electrospinning process and cross-linking in the electrospun chitosan thermal stability was evaluated. Up to three degradation steps were observed in the TG data, corresponding to water dehydration reaction at temperatures below 100 °C, loss of side groups formed between the amine groups of chitosan and trifluoroacetic acid between 150 and 270 °C and chitosan thermal degradation that starts around 250 °C and goes up to 400 °C. The Kissinger model was employed to evaluate the activation energies of the electrospun membranes during isothermal experiments and revealed that thermal degradation activation energy increases for the samples processed by electrospinning and subsequent neutralization and cross-linking treatments with respect to the neat chitosan powder. © 2014 Akadémiai Kiadó, Budapest, Hungary.