Following supramolecular synthon rationale in the context of crystal engineering, a nonsteroidal-anti-inflammatory-drug (NSAID), namely flufenamic acid (FA) and its β-alanine monopeptide derivative (FM), were converted to a series of primary ammonium monocarboxylate (PAM) salts. Majority of the PAM salts (∼90%) showed gelation with various solvents including water and methyl salicylate (important solvents in topical gel formulation). Structure–property correlation studies based on single-crystal X-ray diffraction (SXRD) and powder X-ray diffraction (PXRD) data provided intriguing insights into the structure of the gel network. Furthermore, one of the gelator salts (S7) displayed anticancer activity on a highly aggressive human breast cancer cell line (MDA-MB-231) ,as revealed by MTT, PEG2, and cell migration assays.