Hematite (α-Fe2O3) polycrystalline thin films of different thicknesses were produced by thermal oxidation in air atmosphere from Fe metallic thin-films deposited by radio frequency (RF) sputtering technique. X-ray diffraction (XRD) patterns confirm the formation of hematite phase in all samples and indicate that the mean grain size decreases as the film thickness becomes thinner. Conversion electron Mössbauer spectroscopy (CEMS) spectra at room temperature show magnetic splitting (six line patterns). It is determined that the resonance peaks become broader and asymmetric as the film thickness decreases. This finding was associated with the structural disorder introduced by the thickness reduction. Magnetization as a function of the magnetic field curve obtained at 300 K shows the presence of a weak-ferromagnetic contribution, which was assigned to the large density of decompensated spins at the films surface. From the magnetization vs. temperature curves it has been determined that the Morin transition temperature (TM) is shifted from ∼ 240 K to ∼ 196 K, meanwhile it becomes more broadened as the film thickness decreases. X-ray photoelectron spectroscopy (XPS) measurements show the presence of Fe2+ ions coexisting with Fe3+ ions whose population increases as the film becomes thinner. The density of chemisorbed oxygen increases as the film thickness is reduced in agreement with the results obtained from the other measurements in this work.