Adlayers of ZnOEP were prepared on reconstructed Au(100)-(hex) and unreconstructed Au(100)-(1 x 1) surfaces by immersing into a benzene solution containing ZnOEP molecules, and the adlayer structures were characterized by scanning tunneling microscopy (STM). A hexagonally arranged ZnOEP array was formed on an Au(100)-(hex) surface, whereas a rectangularly arranged ZnOEP array was found on an Au(100)-(1 x 1) surface. The adlayer structure of ZnOEP was dependent upon the underlying An atomic arrangements. Furthermore, an investigation of the spuramolecular assembly for these modified surfaces was carried out by using an open-cage C-60 derivative (opened C-60). A supramolecular assembled adlayer with a 1:1 composition of opened C-60/ZnOEP was formed on Au(100)-(hex), whereas aggregates of opened C-60 were found on the ZnOEP-modified Au(100)-(1 x 1) surface. Electrochemical responses of opened C-60 were significantly influenced by underlying ZnOEP arrays. This finding suggests that precise control of underlying ZnOEP adlayers with the An atomic structure is important to recognize the opened C-60 on them.