The hierarchical assemblies of supramolecules, which consisted of polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) with 3-pentadecyl phenol (PDP) hydrogen-bonded to the 4VP, were investigated in thin films after solvent annealing in a chloroform atmosphere. The synergistic coassembly of PS-b-P4VP and PDP was utilized to generate oriented hierarchical structures in thin films. Hierarchical assemblies, including lamellae-within-lamellae and cylinders-within-lamellae, were simultaneously ordered and oriented from a few to several tens of nanometers over macroscopic length scales. The macroscopic orientation of supramolecular assembly depends on the P4VP(PDP) fraction and can be tailored by varying the PDP to P4VP ratio without interfering with the supramolecular morphologies. The lamellar and cylindrical microdomains, with a periodicity of similar to 40 nm, could be oriented normal to the Surface, while the assembly of comb blocks, P4VP(PDP), with a periodicity of similar to 4 nm, were oriented parallel to the surface. Furthermore, using one PS-b-P4VP copolymer, thin films with different hierarchical structures, i.e., lamellae-within-lamellae and cylinders-within-lamellae, were obtained by varying the ratio of PDP to 4VP units. The concepts described in these studies can be potentially applied to other BCP-based supramolecular thin films, thus creating an avenue to functional, hierarchically ordered thin films.