Frustrated Lewis pairs (FLPs) have been one of the prime contributors toward the development of main-group chemistry in the past few decades. The idea that sterically hindered, unquenched Lewis acid–base pair could be utilized to cleave the H–H bond in H2, has fueled a great deal of research in this domain. Since then, FLP chemistry has gathered considerable scientific inputs and has prompted several investigations into small molecule activation and metal-free catalytic protocols. This chapter is crafted with the air to provide researchers with a concise yet overall concept of FLPs. We begin with a general understanding of the importance of catalysis in small molecule activation and bond formation and how the quest for the same budded the concept of FLPs. Followed by this, a necessary discussion about the basic concept of FLPs along with some principal historical milestones in the field has been included. Subsequently, synthetic strategies to access these molecular catalysts with industrial importance are summarized. These include synthesis of classical FLPs and advanced phosphorous, nitrogen and carbine-based FLPs. Several examples of practical applications, where FLPs have been employed as catalysts, are incorporated. These include hydroboration, hydroarylation, hydrosilylation, polymerization, transfer hydrogenations, amination and N–H activation. Concluding remarks including extension of FLP concept to transition metal, rare earth elements and MOFs are added at the epilogue of this chapter.