The iron-doped TiO 2 nano-composites prepared by sol–gel method and calcined at 923K have been investigated by means of Mössbauer spectroscopy, X-ray diffraction and transmission electron microscopy. The results indicate that TiO 2 exists mainly in the form of anatase phase with a grain size of about 10–20nm. Only about 1.5wt% Fe incorporates into the lattice of anatase and forms a substitutional Fe 0.02 Ti 0.98 O 2 solid solution for all samples. We present that a superparamagnetic α-Fe 2 O 3 phase is produced in iron-doped TiO 2 nano-composites. There is a maximum of 4.0wt% Fe in the superparamagnetic α-Fe 2 O 3 in the doping content of 10wt% Fe, and the amount of ferromagnetic α-Fe 2 O 3 increases largely with the iron-doped concentration. We propose that the Fe sites in the iron-doped TiO 2 are composed of substitutional Fe x Ti 1− x O 2 , superparamagnetic α-Fe 2 O 3 and ferromagnetic α-Fe 2 O 3 .