Friction on Au(100) surfaces has been studied by atomic force microscopy under electrochemical control. Atomic-scale stick-slip pattern in the lateral force signal reveal changes in the surface structure upon changing electrochemical potential, in particular between the hexagonal reconstruction and the Au(100)-(1 × 1) structure. Friction on Au(100) is higher on its (1 × 1) structure than on its hexagonal reconstruction. The frictional response after switching between the two structures is delayed due to the necessary surface reorganization. Atomic periodicity in the stick-slip pattern indicates that the increased friction on Au(100)-(1 × 1) is not caused by an ordered anion adlayer, but by the open structure of the (100) surface. Friction is highest on the oxidized surface, and can be switched reversibly between high and low values on the oxidized and the reduced surface.