Electrospun Ti-doped alpha-Fe2O3 fibres were synthesized and their properties compared with electrospun alpha-Fe2O3 and TiO2 fibres as reference samples. All samples were characterized with FE SEM (field emission scanning electron microscopy), XRD (X-ray diffraction), Fe-57 Mossbauer, FT-IR (Fourier transform infrared) and UV/Vis/NIR (ultraviolet/visible/near infrared) techniques. Ti-doped alpha-Fe2O3 fibres consisted of the interconnected nanoparticles. These fibres showed a hollow substructure. XRD and Fe-57 Mossbauer spectroscopy showed the titanium cations to be incorporated up to 10 mol% into the alpha-Fe2O3 crystal structure. The incorporation of titanium cations into the alpha-Fe2O3 crystal structure caused changes in the corresponding FT-IR spectra. The band gap values of the electrospun fibres were determined and the photocatalytic degradation of rhodamine B (RhB) with the same fibres was investigated.