The CO2‐assisted oxidative dehydrogenation of light alkanes offers a promising route for converting underutilized resources into valuable chemical feedstocks while addressing environmental challenges associated with CO2 emissions. CO2 plays a dual role in ODH by acting as a mild oxidant that enhances product selectivity and catalyst stability while preventing carbon deposition through RWGS and Boudouard reactions. The review has elucidated a variety of catalyst design and optimization strategies that may guide the future development of novel CO2‐assisted ODH catalysts with improved alkane conversion, superior alkene selectivity, and long‐term stability. It provides a comprehensive analysis of the structural characteristics, catalytic performances, and reaction mechanisms of typical catalysts. Special attention is given to the structure‐performance relationship of these catalysts, emphasizing how changes in promoters, supports, and morphology affect critical properties such as redox behavior, acidity‐basicity balance, dispersion of active components, and catalyst‐support interactions. Finally, future research directions and perspectives for the CO2‐assisted ODH of ethane and propane are proposed, with a focus on advancing catalyst design and optimization strategies. This review aims to serve as a comprehensive reference for researchers exploring the potential of CO2‐assisted ODH in promoting sustainable production of light alkenes.