We have examined hierarchical supramolecular structure in the formation of colloidal arrays by immobilizing monodispersed naphthalene-functionalized colloids onto Au substrates bearing viologen moieties using the macrocyclic host molecule cucurbit[8]uril as a supramolecular "handcuff". Naphthalene-functionalized poly(methyl methacrylate)- and polystyrene-based colloids were synthesized by soap-tree emulsion polymerization and characterized by dynamic light scattering and scanning electron microscopy to realize the colloidal arrays and to facilitate direct macroscopic imaging. The formation of host-stabilized ternary complexes on the surface of naphthalene-functionalized microspheres in colloidal suspension was Verified by titration of a preformed viologen CB[8] complex and followed by zeta potential measurements. Patterned self-assembled monolayers of a viologen derivative on Au substrates were formed by backfilling viologen-modified thiols after spontaneous chemisorption of "protective" alkylthiols by microcontact printing. After the initial complexation of CB[8] onto the viologen derivative on the Au substrates, monolayers of colloids with both ID and 2D patterns could be formed and characterized by contact angle measurement. optical microscopy. and scanning electron microscopy. Control experiments indicated that no colloids were attached to the Au substrate after moderate washing by water if) CB[8] was replaced by a smaller analogue of the macrocyclic host, CB[6] or CB[7], (2) colloids without naphthalene-functionalities on the periphery were employed, or (3) alkanethiol was used entirely instead of viologenthiol to protect the Au substrate. These results suggest that the supramolecular ternary complexes were key to successfully bind the colloids onto the Au substrates with the CB[8] acts as a supramolecular "handcuff". The fundamental expertise gained from the study of these materials is believed to facilitate progress in the field of smart materials and wet nanotechnology and lead to the preparation of controlled reversible architectures on surfaces.