Catalysts based on rare earth complexes such as CeO2/2CeF3, Sm2O3/4CeF3, Nd2O3/4CeF3 and Y2O3/4CeF3 were prepared. These catalysts were active for the oxidative dehydrogenation of propane with very high selectivity to propene. At 500-degrees-C and 6000 h-1, using CeO2/2CeF3 as the catalyst, the conversion of propane was 41.3%, selectivity to propene reached 81.1%, propene yield was 33.5%. XRD results indicated that F- and O2- were exchanged in the lattices. Raman spectra showed that the O2- might be the active oxygen species in propane oxidative dehydrogenation.