In-situ scanning tunneling microscopy (STM) and cyclic voltammetry have been employed to investigate conformation-related adlayer structures of four calixarenes, three calix[4]arenes with specific conformations and one calix[6]arene. All the molecules form ordered adlayers on the Au(111) surface in 0.1 M HClO4 under the potential control. For calix[4]arenes, different adlayers are organized on the basis of their specific conformations, indicating that conformations might be used to obtain desired structures. A well-defined adlayer is observed for calix[6]arene. The results demonstrate that the conformation of calixarenes can be immobilized on the Au(I 11) surface through adsorption, although various conformations of the molecule are reported in solution. The reason is ascribed to the intermolecular and molecule-substrate interactions. On the basis of high-resolution STM images, structural models are tentatively proposed for the ordered adlayers of calixarenes.