We show in this work that the internal photoemission at the semiconductor‐insulator interface in the semiconductor‐insulator‐electrolyte system can be used to initiate localized chemical reactions at the insulator‐electrolyte interface. Using this concept, successful depositions of Cu and Ni films have been obtained on oxidized Si wafers. We have also found that the activation of the SiO2surface with Pd atoms results in an efficient electron transfer at the SiO2‐electrolyte interface and improves the adhesion of the deposited metal.