Catalysis plays a crucial role in advancing sustainability. The unique reactivity of frustrated Lewis pairs (FLPs) is driving an ever-growing interest in the transition metal-free transformation of small molecules like CO 2 into valuable products. In this area, there is a recent growing incentive to heterogenize molecular FLPs into porous solids, merging the benefits of homogeneous and heterogeneous catalysis - high activity, selectivity, and recyclability. Despite the progress, challenges remain in preventing deactivation, poisoning, and simplifying catalyst-product separation. This review explores the expanding field of FLPs in catalysis, covering existing molecular FLPs for CO 2 hydrogenation and recent efforts to design heterogeneous porous systems from both experimental and theoretical perspectives. Section 2 discusses experimental examples of CO 2 hydrogenation by molecular FLPs, starting with stoichiometric reactions and advancing to catalytic ones. It then examines attempts to immobilize FLPs in porous matrices, including siliceous solids, metal-organic frameworks (MOFs), covalent organic frameworks, and disordered polymers, highlighting current limitations and challenges. Section 3 then reviews computational studies on the mechanistic details of CO 2 hydrogenation, focusing on H 2 splitting and hydride/proton transfer steps, summarizing efforts to establish structure-activity relationships. It also covers the computational aspects on grafting FLPs inside MOFs. Finally, Section 4 summarizes the main design principles established so far, while addressing the complexities of translating computational approaches into the experimental realm, particularly in heterogeneous systems. This section underscores the need to strengthen the dialogue between theoretical and experimental approaches in this field.