The outstanding capability of Frustrated Lewis Pair (FLP) catalysts to activate small molecules has gained significant attention in recent times. Reactivity of FLP is further extended toward the hydrogenation of various unsaturated species. Over the past decade, this unique catalysis concept has been successfully expanded to heterogeneous catalysis as well. The present review article gives a brief survey on several studies on this field. A thorough discussion on quantum chemical studies concerning the activation of H2 is provided. The role of aromaticity and boron-ligand cooperation on the reactivity of FLP is discussed in the Review. How FLP can activate other small molecules by cooperative action of its Lewis centers is also discussed. Further, the discussion is shifted to the hydrogenation of various unsaturated species and the mechanism regarding this process. It also discusses the latest theoretical advancements in the application of FLP in heterogeneous catalysis across various domains, such as two-dimensional materials, functionalized surfaces, and metal oxides. A deeper understanding of the catalytic process may assist in devising new heterogeneous FLP catalysts through experimental design.