Ag nanoparticles (d = ca. 20 nm) adsorbed on the surface of a glass plate immersed in pure water dissolved when white light was irradiated under application of an external electric field. Dissolution was monitored via change in absorption spectrum. Structural characterization revealed that the number of Ag nanoparticles on the glass decreased as a consequence of the treatment. The size of the particles, however, increased to ca. 80 nm following the treatment. The rate of change in the structure was dependent on both the irradiated light intensity and the existence of an external electric field. These results demonstrate that photoinduced structural change of Ag nanoparticles on an insulating material is accelerated by an external electric field in solution.