The molecular motion of surface-immobilized double-decker phthalocyanine complexes was examined using STM. (C8OPc)(2)Ce (1), (C12OPc)(2)Ce (2), and (C8OPc)Ce(Pc) (3) double-decker complexes, of which two ligands contained PC nuclei, formed well-ordered self-organized structures on their own. Square-shaped top Pc ligands were clearly observed for complexes 1, 2, and 3 even though free space presented around the top ligands caused by mixing the complexes with template molecules. However, the details of the shapes of the top ligands of complexes 1, 2, and 3 were changed by the surrounding environment. The surrounding environment was considered to have influenced the mobility of the top ligands. Another complex, (C8OPc)Ce(TPP) (4), had difficulty forming a self-organized structure by itself. Complex 4 could have been immobilized by coadsorbing on the substrate with the C8OPc template, but the intramolecular structure of the top ligands of complex 4 was difficult to observe. The results strongly suggested that combinations of molecules composed of double-decker complexes as well as the free space presented around a top ligand are important factors that control the molecular motion of immobilized double-decker complexes on solid surfaces.