Silver(Ag) nanostructures demonstrate outstanding optical, electrical, magnetic, and catalytic properties and are utilized in photonic, energy, sensors, and biomedical devices.The target application and the performance can be inherently tuned by control of configuration, shape, and size of Ag nanostructures. In this work, we demonstrate the systematical fabrication of various configurations of Ag nanostructures on sapphire(0001) by controlling the Ag deposition thickness at different annealing environments in a plasma ion coater. In particular, the evolution of Ag particles(between 2 and 20 nm),irregular nanoclusters(between 30 and 60 nm), and nanocluster networks(between 80 and 200 nm) are found be depended on the thickness of Ag thin film. The results were systematically analyzed and explained based on the solid-state dewetting,surface diffusion, Volmer–Weber growth model, coalescence,and surface energy minimization mechanism. The growth behavior of Ag nanostructures is remarkably differentiated at higher annealing temperature(750 ℃) due to the sublimation and temperature-dependent characteristic of dewetting process.In addition, Raman and reflectance spectra analyses reveal that optical properties of Ag nanostructures depend on their morphology. Silver (Ag) nanostructures demonstrated outstanding optical, electrical, magnetic, and catalytic properties and are utilized in photonic, energy, sensors, and biomedical devices. The target application and the performance can be inherently tuned by control of configuration, shape, and size of Ag nanostructures. We demonstrate the systematical fabrication of various configurations of Ag nanostructures on sapphire (0001) by controlling the Ag deposition thickness at different annealing environments in a plasma ion coater. In particular, the evolution of Ag particles (between 2 and 20 nm), irregular nanoclusters (between 30 and 60 nm), and nanocluster networks (between 80 and 200 nm) are found be depended on the thickness of Ag thin film. The results were systematically analyzed and explained based on the solid-state dewetting, surface diffusion, Volmer-Weber growth model, coalescence, and surface energy minimization mechanism. The growth behavior of Ag nanostructures is remarkably differentiated at higher annealing temperature (750 ° C) due to the sublimation and temperature-dependent characteristic of dewetting process. In addition, Raman and reflectance spectra analyzes reveal that optical properties of Ag nanostructures depend on their morphology.