Nanosized CeNbNiO catalysts have been prepared by a modified sol-gel method and investigated in the oxidative dehydrogenation of propane to propene (ODHP). The addition of Nb into NiO can enhance the propene selectivity, while Ce introduction can largely increase propane conversion at low temperature. With 1.5Ce3NbNiO catalyst, a propene yield of 10.4% was obtained at 250 degrees C. XRD, N-2-adsorption, H-2-TPR, XPS, O-2-TPD, NH3-TPD and pulse reaction have been performed to study the intrinsic difference between these NiO-based catalysts. A strong interaction between Ni and Ce/Nb species was clearly evidenced for the doped NiO samples. The doped elements affected greatly the catalyst properties such as surface acidity and the reactivity of oxygen species, which are closely related to the catalytic performance of the catalysts.