The catalytic performance and characterization of YBa2Cu3O7-δ and YBa2Cu3O7-δXσ for the oxidative dehydrogenation of ethane (ODE) to ethene have been investigated. Under the reaction conditions of temperature=680℃, C2H6/O2/N2 molar ratioD2/1/3.7, and contact timeD1.67£10¡4hgml¡1, YBa2Cu3O7¡0.21F0.16 showed 84.1% C2H6 conversion, 81.8% C2H4 selectivity, and 68.8% C2H4 yield; YBa2Cu3O7¡0.18Cl0.13 showed 92.5% C2H6 conversion, 72.0% C2H4 selectivity, and 66.6% C2H4 yield. The sustainable performance during a period of 40h on-stream reaction at 680℃ demonstrated that the F- and Cl-doped catalysts are durable. X-ray powder diffraction results indicated that the undoped YBa2Cu3O7-δ and halide-doped YBa2Cu3O7-δXσ were of triple-layered oxygen-deficient perovskite-type orthorhombic structure. The results of the X-ray photoelectron spectroscopy, thermal treatment, thermogravimetric analysis, and 18O2-pulsing studies indicated that the incorporation of halide ions into the YBa2Cu3O7-δ lattice enhanced the activity of lattice oxygen. According to the O2 temperature-programmed desorption and temperature-programmed reduction results, we conclude that the oxygen species desorbed at 610-710℃ are active for the selective oxidation of ethane and those desorbed below 610℃ are active for the total oxidation of ethane; a suitable oxygen nonstoichiometry and Cu3C concentration in YBa2Cu3O7-δXσare required for the best catalytic performance of the catalysts.