Self-assembled silver, gold, and copper nanostructures on the monocrystalline GaAs (100) wafer surface were obtained via physical vapor deposition and characterized by optical reflection spectroscopy, scanning electron microscopy, and current-voltage curve measurements. Reflection spectra of the samples with Ag equivalent thicknesses of 2, 5, 7.5, and 10 nm demonstrated wide plasmonic bands in the visible range of spectra. Thermal annealing of the nanostructures led to narrowing of the plasmonic bands of Au and Ag nanostructures caused by major transformations of the film morphology. While the as prepared films predominantly had a small scale labyrinth structure, after annealing well-separated nanoislands are formed on the gallium arsenide surface. A clear correlation between films morphology and their optical and electrical properties is elucidated. Annealing of the GaAs substrate with Ag nanostructures at 100 °C under control of the resistivity allowed us to obtain and fix the structure at the percolation threshold. It is established that the samples at the percolation threshold possess the properties of resistance switching and hysteresis.