Supramolecular assembly (SMA) of block copolymer and small molecule has received enormous research interest for its applications in high resolution surface patterning of different functional nanomaterials at different length scales. The patternability of block copolymer supramolecular system results from its ability to self-assemble into a wide range of periodic structures in nanoscopic length scale. The advantages of using supramolecular system over the pure block copolymer are easy tuning of morphology by changing the small molecule composition, introduction of new functionality into the block copolymer layer by using non-covalent interaction and simple removal of the minor component by dissolution from the block copolymer layer to transform it into a porous nanotemplate. In the last few years, our group has extensively studied block copolymer–small molecule supramolecular assembly in thin film and developed some novel SMA systems mostly with an aim to fabricate polymer nanotemplates for further surface patterning with various functional nanomaterials. In this feature article, we will discuss these recent developments in creating such patterns of various functional nanomaterials using block copolymer supramolecular assembly.