Metal selective co-ordinative nanostructures were constructed by the supramolecular co-assembly of pyridine appended TTF (TTF-Py) and pyrene (PYR-Py) derivatives in appropriate solvent composition mixtures with metal ions.Microscopic analyses show that TTF-Py shows distinctive morphology with either of these metal ions, forming I-D tapes with 1:1 Pb2+ complex and 2-D sheets with 1:2 Zn2+ complex. A rationale has been provided from molecular level packing for such hierarchical changes. In case of Cu2+, we have observed an anomalous binding of metal ion to the core sulphur groups causing redox changes in the TTF core. PYR-Py on the other hand is shown to be a fluorescent sensor for Pb2+, Zn2+, Hg2+ and Ag+. With different fluorescent response for metal complexes, we essentially obtained similar 1-D assemblies suggesting similar binding modes for all of them. Supramolecular approach through which morphology of an electron donor moiety can be engineered by metal ions can be a new tool in nanoelectronics.