Ultra-thin fibre assemblies consisting of cellulose were prepared by means of the electrospinning procedure. In this study, cellulose acetate (CA) was dissolved in dimethylacetamide/acetone (2:1 v/v) and electrospun using a high voltage of 10 and 15 kV and a tip to collector distance of 15 cm. The CA fibre mats were deacetylated and chemically modified by means of a 1,2,3,4-butanetetracarboxylic acid (BTCA)/sodium hypophosphite and a BTCA/(3-aminopropyl)triethoxysilane (APTES) solution. After a thermal treatment at 180°C, Fourier Transform infrared/attenuated reflection spectra of the cross-linked fibre mats confirmed the formation of an ester linkage and an imide moiety, respectively. X-ray diffraction spectra made evident the presence of cellulose II. Thermogravimetric analysis indicated a significant increase in the thermal stability of the chemically modified mats. The water vapour transmission is increased for BTCA/APTES fibre mats.