An experimental procedure for Au(111) single crystalline substrate fabrication on mica is described with its know-how from the preparation of cleaved mica and gold wires through annealing process in air. Relation between etch pit formation in a self-assembled monolayer (SAM) and 22 × √3 surface reconstruction is briefly overviewed. A new surface-reconstructed structure on Au(111) was confirmed and an etch-pit-free SAM was obtained on the surface for the first time. This new Au(111) surface will open a new field in fundamental surface studies and applications of SAM.