Abstract The system Au/Si(100) has been studied using LEED and AES. Au films grow as Au(111) | Si(100) having six azimuthally rotated orientations at low deposition temperatures below 50°C after the formation of intermediate gold suicide layers. Crystalline gold silicide thin layers are formed on the Au(111) film after heat treatment at 100–400°C. Two types of suicide LEED pattern observed seem to have no correlation with crystallographic data reported on quenched alloy films. Heat treatment over 450°C leads to agglomeration of the film, producing a series of Au-induced superstructures. Heat treatment of the Au film over 1000°C regenerates the clean Si surface accompanied with many etch pits.