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Plasmonic chemistry converts metal nanostructures into photocatalysts via three interconnected channels at the molecule–metal interface: enhanced near fields, nonequilibrium charge carriers, and localized heat. This review focuses on this interfacial perspective. We show how adsorbates and ligands do more than just stick to nanoparticles – they reduce plasmon lifetimes, change work functions, modify the density of states, and impact the energy and charge flow during various physical processes. Ultrafast thermalization under pulsed excitation and steady state conditions under continuous illumination open up different pathways for chemical reactions. Although the plasmonic metal is crucial, surface-bound molecules actively participate by scavenging charge carriers, affecting selectivity and stability, and even undergoing chemical transformations. These aspects are crucial for controlling product distributions and enabling novel chemical pathways by exploiting excited-state pathways inaccessible through thermal energy. Together with the nanoscale properties of plasmonic nanostructures, chemical reactions can be confined to nanoscale hot spots shaped by geometry and polarization. These insights inform the development of practical design principles for antenna–reactor hybrids and novel plasmonic materials in which absorption, carrier localization, and interfacial alignment are precisely engineered. Finally, we identify key open questions and the need for operando interfacial techniques to transform these insights into practical tools for selective, solar-driven synthesis.