This chapter reviews the existing opportunities for the conversion of carbon dioxide (CO₂) into value-added organic compounds of higher complexity. More specifically it intends to provide an overview of the progress made throughout the years in the direct activation of CO₂ by showcasing some of the most important structurally characterized CO₂ complexes, the principal binding modes and the use of this knowledge to serve our current and future need for organic precursors, intermediates and materials. For completion, beside metal-mediated procedures also some organocatalytic ones are described, and an outlook based on the current state-of-the-art is provided to point at the importance of catalysis as a key technology for sustainable development.