Pursuit of high catalytic selectivity is paramount in the design of catalysts for green chemical processes towards minimizing the production of undesired products. We demonstrated that catalytic selectivity for production of alkene through oxidative dehydrogenation of alkane on transition metal oxides can be promoted through tailoring the surface lattice of the oxide catalyst. Selectivity for production of ethylene through oxidative dehydrogenation (ODH) of ethane on Co3O4 nanocrystals can be substantially increased by 30%-35% via temperature-mediated reconstruction of surface lattice of Co3O4. Co3O4 nanocrystals formed at 800 degrees C leads to smooth, flat crystal plane with predominantly exposed (111) facet in contrast to high Miller index (311) facet of Co3O4 formed at <= 700 degrees C, revealed by environmental transmission electron microscopy. Isotope-labelled experiments suggest that the higher catalytic selectivity on the (111) facet results from the lower activity of its surface lattice oxygen atoms. Consistent with these experimental results, DFT calculations suggest low activity of surface lattice oxygen atoms and high activation barriers for adsorption and dissociation of C-H bond on the (111) surface in contrast to (311). Upon the activation of C-H on (311), the stronger binding of ethylene on more active, under coordinated surface lattice oxygen atoms of (311) forms a robust "deprotonated ethylene glycol"-like intermediate on (311) with a rate-limiting desorption barrier to the formation of ethylene. Compared to (311), the kinetically favorable desorption of bound ethylene species from (111) surface well rationalized the higher selectivity for production of ethylene on (111) than (311). These findings demonstrate that temperature-mediated tailoring of the surface lattice for a transition metal oxide nanocatalyst is a promising approach in pursuing high selectivity in oxidative dehydrogenation of hydrocarbons.