We report herein the preparation, characterization, and catalytic performance of a series of heterogeneous catalysts featuring highly dispersed zinc sites on zeolitic SSZ-13 and ZSM-5 frameworks. The materials are evaluated in the CO₂-assisted oxidative ethane dehydrogenation, a very important reaction for the synthesis of platform chemicals. In particular, we find that Zn_2.92/SSZ-13 exhibits high reactivity in the conversion of C₂H₆ and CO₂ and high ethene selectivity. In line with the experimental results, we show that the selective character of the catalyst is due to the characteristic compositional structure of the support and its topology that can effectively confine CO₂ molecules. An in-depth molecular analysis via operando studies and DFT calculations shows that the rate-limiting step of the reaction with CO₂ is the second C–H bond dissociation to give C₂H₄. The addition of CO₂ effectively reduces the energy barrier of this step, favoring desorption of C₂H₄ while limiting byproduct formation. Overall, this work demonstrates the breakthrough potential of catalysts made of highly dispersed zinc species on zeolites in relevant transformations.