Charge-transfer complexes of a disk-shaped electron-rich donor, based on pentakis(phenylethynyl)phenol and a series of electron-deficient acceptors, based on 2,4,7-trinitro-9-fluorenone have been prepared. Specific interactions resulted in supramolecular assemblies that exhibited various mesophases, although none of the pure materials showed liquid crystalline properties. Complexes of the low molar mass donor with a weak, intermediate, and a strong acceptor exhibited N-D, N-Col, and Col(h) phases, respectively, as well as strong increases in the melting and clearing temperatures. Complexes with the corresponding macromolecular donor showed the nematic lateral (NL) phase. In addition, suppression of crystallization led to mesophases stable over a wide temperature range. The use of a polymer bound mesogens and charge-transfer complexing are effective tools to induce a wide variety of unusual mesophases, starting from a limited number of materials.