Supramolecular synthon approach was employed to synthesize a series of primary ammonium monocarboxylate (PAM) salts derived from a well-known nonsteroidal anti-inflammatory drug (NSAID) naproxen (NAP) and its amino acid conjugates namely naproxen-L-phenylalanine (NAP-PHE) and naproxen-L-alanine (NAP-ALA), and four amines namely tyramine (TYRM), tryptamine (TRPM), 3,4-dimethoxyphenethylamine (DMP) and phenethylamine (PEA) as potential supramolecular gelators for developing self-drug delivery system. Out of the total twelve PAM salts thus synthesized, 75 % of the salts showed gelation ability. Importantly, majority of the gelator salts (67 %) displayed gelling abilities with topical gel formulating solvent methyl salicylate. One such salt, NAP-PHE⋅PEA was an ambidextrous gelator producing hydrogel with pure water and organogel with methyl salicylate with a minimum gelator concentration (MGC) of 0.5 wt % (w/v) thereby qualifying as a supergelator. The gels were extensively characterized by dynamic rheology and transmission electron microscopy (TEM). Supramolecular interactions such as π-π and C-H…π were probed by variable-temperature