The growth of metal nanostructures induced by surface plasmons has attracted widespread attention and provides a wide range of applications in the development of plasmonic nanochemistry, biosensors, photoelectrochemical coupling reactions, etc. Herein, a simple method is reported for the fabrication of Ag nanoflakes induced by the surface plasma on two-dimensional periodic nanopatterned arrays with the aid of 4-MBA molecules. The light radiation, molecules, and environmental gases are selected to track the formation mechanism of Ag nanoflakes. The in situ Raman observations and theoretical analyses confirm that small aromatic molecules with carboxyl groups play important roles in Ag nanoflake formation derived by localized surface plasmon resonance (LSPR)-driven carriers, which provide profound insights into the study of LSPR-driven carriers, participating in chemical reactions and the reconstruction of dense hot spots in nanogaps.