Block copolymer supramolecular assemblies (SMAs) have been used to prepare nanotemplates and nanoarrays of a variety of materials. This has been achieved via selective H-bonds between a low molecular weight additive and one block of the block copolymer. Herein we propose to extend the range of the additives by exploring multiple weak interactions other than hydrogen bonding. This is illustrated with the following SMA: diblock copolymer poly(styrene-b-4-vinylpyridine) (PS-b-P4VP) and the low molecular weight additive 1,5-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-1,6-methano[10]annulene (bisEDOT), a molecule synthesized specifically for this project. Through rational design, bisEDOT possesses several characteristics which make it a suitable candidate for functional SMA formed without hydrogen bonds. It has multiple sites for SMA formation, exhibits photoluminescence, and is a precursor to an electroconductive polymer. Also, removal of bisEDOT results in porous thin films allowing us to study the morphology using AFM. C-AFM confirms that polymerization of bisEDOT leads to electroconductive polymer thin films. In this work, we discuss the formation of this SMA as well as in situ polymerization of bisEDOT in SMA thin films.