Plasmonic catalysis is an ever-growing field in which chemical reactions are enabled by visible light excitation. The plasmonic effects provide a unique reaction environment, which can greatly affect chemical reaction processes. On the basis of extensive research on plasmon-induced chemical reactions, we focus on the fundamentals of plasmon-mediated catalytic selectivity and summarize recent advances and emerging opportunities in selective chemical bond evolution in this perspective. Taking representative reactions as examples, the unique feature and advantage of surface plasmons in modulating reaction selectivity are deciphered from the perspective of the three elementary steps: adsorption of reactants, activation of adsorbates, and desorption of products. In addition, nanoconfined plasmon-induced spatially selective reactions are also included. This perspective informs insights and opportunities for rationally engineering plasmonic catalytic systems toward purposeful solar energy utilization.