LAUSR

The collective oscillation of free electrons at the nanoscale surface of gold nanostructures is closely modulated by tuning the size, shape/morphology, phase, composition, hybridization, assembly, and nanopatterning, along with the surroundings of the plasmonic surface located at a dielectric interface with air, liquid, and solid. This review first introduces the physical origin of the intrinsic optical properties of gold nanostructures and further summarizes stimuli‐responsive changes in optical properties, metal‐field‐enhanced optical signals, luminescence spectral shaping, chiroptical response, and photogenerated hot carriers. The current success in the landscape of nanoscience and nanotechnology mainly originates from the abundant optical properties of gold nanostructures in the thermodynamically stable face‐centered cubic (fcc) phase. It has been further extended by crystal phase engineering to prepare thermodynamically unfavorable phases (e.g., kinetically stable) and heterophases to modulate their intriguing phase‐dependent optical properties. A broad range of promising applications, including but not limited to full‐color displays, solar energy harvesting, photochemical reactions, optical sensing, and microscopic/biomedical imaging, have fostered parallel research on the multitude of physical effects occurring in gold nanostructures.