(Figure Presented) Celling together: The alternate coassembly of a noncovalent donor-acceptor (D-A) amphiphilic pair in water results in very long nanofibers that form hydrogels (see scheme). Microscopic and single-crystal studies have provided an insight into the hierarchical self-assembly of the chargetransfer (CT) amphiphile, which consists of coronene and a viologen derivative, into cylindrical micelles and gels as the concentration of the D-A pair is increased. © 2010 Wiley-VCH Verlag GmbH & Co. KGaA.