In this work, hollow "spindle-like" alpha-Fe2O3 nanoparticles were synthesized by a hydrothermal route. The Ag/alpha-Fe2O3 catalyst was prepared based on the spindle-shaped alpha-Fe2O3 with CTAB as the surfactant, which showed excellent photoelectric property and photocatalytic activity. The structural properties of these samples were systematically investigated by X-ray powder diffraction, scanning electronic microscopy, transmission electronic microscopy, energy-dispersive X-ray spectra, and UV-Vis diffuse reflectance spectroscopy techniques. The photo-induced charge separation in the samples was demonstrated by surface photovoltage measurement. The photocatalytic performances of the Ag/alpha-Fe2O3 and alpha-Fe2O3 samples were comparatively studied in the degradation of toluene under xenon lamp irradiation by in situ FTIR spectroscopy. Benzaldehyde and benzoic acid species could be observed on the alpha-Fe2O3 surface rather than Ag/alpha-Fe2O3 surface. The results indicate that the Ag/alpha-Fe2O3 sample exhibited higher photocatalytic efficiency. (C) 2012 Elsevier Ltd. All rights reserved.