We report the rational design and synthesis of a supramolecular gelator based on a Zn(II)–salophen derivative functionalized with L-valine residues. This compound is able to gelate acetonitrile by self-assembly into helical long fibers that further aggregate into bundles. The fibers are stabilized by a network of hydrogen bonds and π–π stacking interactions established by gelator units stacked one on the top of another. The gel is responsive to the presence of anions. Moreover the zinc center remains available for the coordination of an external guest without causing gel disruption.