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Frustrated Lewis pairs (FLPs) combine a Lewis acid, an electron pair acceptor, and a Lewis base, an electron-pair donor, to access unique chemistry. Steric encumbrance of both components is utilised to prevent classical Lewis adduct formation, which preserves the reactivity of both the Lewis acidic and Lewis basic moieties and allows for synergistic activation of a plethora of small molecules, most notably H2 and CO2. This reactivity has been successfully applied to achieve metal-free hydrogenation of a variety of substrates including imines, ketones, and alkenes. However, the exact mechanism by which FLP systems activate small molecules is still a topic of debate. Gaining mechanistic insight into the functioning of these systems is of great importance to further explore their unique chemistry and unlock their full potential as organocatalysts. In this PhD thesis entitled “Radicals and London dispersion in frustrated Lewis pair chemistry” two highly important aspects that influence the mechanism and reactivity of FLP systems have been discussed: radical formation, and London dispersion forces. Firstly, a combination of experimental and computational analysis is used to demonstrate the different conditions under which radical formation within FLP systems occurs. Next, the influence of London dispersion on chemical transformation is examined, focusing on the formation of van der Waals complexes within FLP systems and effect this has on FLP reactivity.