The CO2-assisted oxidative dehydrogenation (ODH) 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 the Reverse Water-Gas Shift (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, including transition metal catalysts (e. g., Cr-based, Co-based, V-based), metal oxide catalysts (e. g., Ga-based, In-based), noble metal catalysts (e. g., Pt-based, Ru-based), and bimetallic 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.