Cr-doped alpha-Fe(2)O(3)fibres were synthesized by combining electrospinning and the thermal treatment of electrospun composite fibres at 500 degrees C. XRD analysis showed the formation of solid solutions with a corresponding small decrease in the unit-cell volume due to a difference between the ionic radii of Fe(3+)and Cr(3+)cations. Mossbauer spectroscopy showed that the incorporation of Cr(3+)into the alpha-Fe(2)O(3)crystal structure induced a decrease in the hyperfine magnetic field. Doping of alpha-Fe(2)O(3)with Cr(3+)also influenced the shape and position of IR bands in relation to reference alpha-Fe(2)O(3)fibres in the corresponding FT-IR spectra. The FE-SEM images of Cr-doped alpha-Fe(2)O(3)fibres showed that they consisted of interconnected nanoparticles and possessed a hollow substructure. The photocatalytic degradation of rhodamine B using electrospun fibres was also investigated.