In this work, θ-Al2O3 whiskers with twins were successfully fabricated by a hydrothermal method followed by annealing at 1000 °C in argon atmosphere using Al2(SO4)3·18H2O, CO(NH2)2 and PEG2000 as initial materials. It is confirmed that precursor of AlO(OH) whiskers is suitable to be used for preparing alumina whiskers when the molar ratio of Al3+: CO(NH2)2 is selected to be 1:6. The mean length of obtained whiskers is 1.5 μm and the average width is 0.1 μm. Interestingly, it is found that the as-prepared θ-Al2O3 whiskers consist of twins with (100) plane as the twin surface, which is ascribed to the phase transformation from tetragonal phase (δ-Al2O3) to monoclinic phase (θ-Al2O3) during the annealing. Additionally, the specific surface area of θ-Al2O3 whiskers is measured to be 38.2 m2/g.