Ce-incorporated MoVTeNbO catalysts were developed to enhance ethylene productivity of oxidative dehydrogenation of ethane (ODHE) to ethylene. Structural characterizations (XRD, TEM, STEM, Raman, and UV vis DRS) and DFT calculations revealed that Ce atoms were incorporated into MoVTeNbO framework with maintaining its unique structure (M1 phase), which is active phase for ODHE. The reducibility of the catalysts was enhanced and both V5+ and the lattice oxygen species available to ODHE reaction were enriched by incorporation of Ce, confirmed by TPR, XPS, and pulse injection method, respectively. These improved properties enhanced the conversion of ethane while maintaining their excellent selectivity to ethylene for MoVTeNbCeO catalysts. It is noteworthy that 56.2% of ethane conversion and 95.4% of ethylene selectivity were retained for 200 h over MoVTeNbCeO-0.1 catalyst. Ethylene productivity was calculated to be 1.11 kgC(2)H(4)/kg(cat) h. The developed catalyst exhibits substantial level of ethylene productivity and stability having the possibility with low production of COx to make a step forward for industrialization of oxidative dehydrogenation of ethane.