Improvements in the performance of electrocatalysts, along with continuing advances in selective pathway for target reaction, have great potential to offer opportunities in designing competitive reactions especially for using a photophysical process owing to its tunable properties. Herein, we demonstrated a first empirical evidence of suppressing the formation of undesired peroxide intermediate through plasmonic effects, in which plasmonic Ag-Pt bimetallic nanocages were synthesized with an edgeless feature, and a custom-made RDE/RRDE working station was designed to provide unique means by which to in situ realize the plasmon-induced effects toward the target reaction. The edgeless Ag-Pt bimetallic nanocages with hollow interior performed newly plasmion-induced effects, which was characteristic of photodependent nature to suppress the formation of undesired peroxide intermediate. We concluded that the plasmon-induced hot electron transfer governed the suppression of peroxide formation instead of plasmon-induced heating that would, cause a negative effect (i.e., increase of peroxide yield), in which the hot electron. transfer of Ag nanostructure offered a sufficient energy to populate the antibonding orbital O-2, as illustrated by in situ X-ray absorption approach. This rapid light-dependent nature corresponding to localized surface plasmon resonance in present nanocages can potentially offer synergetic strategies toward altering the chemical reactions or reaction pathways in various fields.