AbstractThe activation and functionalization of carbon dioxide entails great interest related to its abundance, low toxicity and associated environmental problems. However, the inertness of CO₂ has posed a challenge towards its efficient conversion to added‐value products. In this review we discuss one of the strategies that have been widely used to capture and activate carbon dioxide, namely the use of donor‐acceptor interactions by partnering a Lewis acidic and a Lewis basic fragment. This type of CO₂ activation resembles that found in metalloenzymes, whose outstanding performance in catalytically transforming carbon dioxide encourages further bioinspired research. We have divided this review into three general sections based on the nature of the active sites: metal‐free examples (mainly formed by frustrated Lewis pairs), main group‐transition metal combinations, and transition metal heterobimetallic complexes. Overall, we discuss one hundred compounds that cooperatively activate carbon dioxide by donor‐acceptor interactions, revealing a wide range of structural motifs.