Ordered templates are of notable interest for the fabrication of highly ordered inorganic/organic nanostructures. In this report, ordered nanotemplates have been prepared using supramolecular assembly (SMA) from diblock copolymer polystyrene‐b‐poly(4‐vinylpyridine) (PS‐b‐P4VP) and 2‐(4‐hydroxyphenylazo) benzoic acid (HABA). HABA selectively associated with P4VP blocks by hydrogen bonds (molar ratio 1:1) and increases the relative volume fraction of P4VP/HABA. Solvent annealing by 1–4 dioxane improves the ordering in thin films of supramolecular assembly. Almost featureless morphology was observed before annealing, though the disordered cylindrical pores were observed on removal of HABA by ethanol. After solvent annealing in 1–4 dioxane, highly dense and hexagonally arranged cylindrical domains were observed perpendicular to the surface of the substrate. Removal of HABA leads to cylindrical pores with an average pore diameter of 15 ±1 nm and periodicity of 35 ± 1 nm. Perpendicularly oriented lamellar structure with a periodicity of □31 nm was obtained when the relative volume fraction of P4VP/HABA was altered to 0.5 by changing the molecular weight of copolymers. This method is very simple as compared to the lithographic process used for templates.