Calix[4]monohydroquinone has been used as a supramolecular system for the generation of NO gas. In a one-electron reduction scheme involving NO+ subsetcalix[4]monohydroquinone complex, NO is released without the presence of an external reducing agent. Free calix[4]monoquinone, thus obtained, can be reused for a new NO-releasing cycle after NaBH4-reduction to calix[4]monohydroquinone.