The sol-gel and hydrothermal methods were adopted to synthesize β-NiMoO₄ and α-NiMoO₄ respectively, which were characterized by XRD and H₂-TPR. Their catalytic performances for oxidative dehydrogenation of propane were tested. The results indicated that the crystal structure of catalysts obtained from different preparation methods was different; thereby there was a great variation in the catalytic performance. The β-NiMoO₄ catalyst prepared by the sol-gel method exhibited the better catalytic performance for oxidative dehydrogenation of propane under the low temperature, over which the propylene yield can attain 9.47% at 450°C, than that of α-NiMoO₄ prepared by the hydrothermal method.