Gold–organic hybrids can be prepared on gold substrates by on‐surface dehalogenation of molecular precursors with multiple halogen substituents. Various contact geometries of covalent arylAu bonds are achieved by changing the halogen substituents in the bay or peri regions. Scanning tunneling microscopy/spectroscopy (STM/STS) investigations allow a better understanding of the structure/property relationships in various gold–aryl contacts. Recent progress on the synthesis, large‐scale alignment, and STS measurement of gold–organic hybrids is described, ending with an emphasis on potential future applications, e.g., as precursors (intermediates) for the synthesis of graphene nanoribbons (GNRs) on insulating surfaces, and as a model system to investigate the role of covalent arylAu bonds in electron transport through gold–GNR contacts. Gold–organic hybrids with various arylAu bonding geometries can be prepared on gold substrates through on‐surface dehalogenation of molecular precursors with multiple halogen substituents. Recent progress made in the synthesis, large‐scale alignment and scanning tunneling spectroscopy of gold–organic hybrids is highlighted.