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Abstract Plasmon-driven photocatalysis offers a unique means of leveraging nanoscale light–matter interactions to convert photon energy into chemical energy in a chemoselective and regioselective manner under mild reaction conditions. Plasmon-driven bond cleavage in molecular adsorbates represents a critical step in virtually all plasmon-mediated photocatalytic reactions and has been identified as the rate-determining step in many cases. This review article summarizes critical insights concerning plasmon-triggered bond-cleaving mechanisms gained through combined experimental and computational efforts over the past decade or so, elaborating on how the plasmon-derived physiochemical effects, metal–adsorbate interactions, and local chemical environments profoundly influence chemoselective bond-cleaving processes in a diverse set of molecular adsorbates ranging from small diatomic molecules to aliphatic and aromatic organic compounds. As demonstrated by several noteworthy examples, insights gained from fundamental mechanistic studies lay a critical knowledge foundation guiding rational design of nanoparticle–adsorbate systems with desired plasmonic molecule-scissoring functions for targeted applications, such as controlled release of molecular cargos, surface coating of solid-state materials, and selective bond activation for polymerization reactions.