Organic salts based on dicyclohexylamine and substituted/unsubstituted cinnamic acid exhibit efficient gelation of organic fluids, including selective gelation of oil from an oil/water mixture. Among the cinnamate salts, dicyclohexylammonium 4-chlorocinnamate (1), 3-chlorocinnamate (2), 4-bromocinnamate (3), 3-bromocinnamate (4), 4-methylcinnamate (5) and the parent cinnamate (6) are gelators, whereas 2-chlorocinnamate (7), 2-bromocinnamate (8), 3-methylcinnamate (9), 2-methylcinnamate (10) and hydrocinnamate (11) are non-gelators. Non-gelation behaviour of 11 and various benzoate derivatives 12–18 indicate the significance of an unsaturated backbone in the gelation behaviour of the cinnamate salts. A structure–property correlation based on the single-crystal structures of most of the gelators (1, 3, 5 and 6) and non-gelators, such as 7, 8, 10–18, indicates that the prerequisite for the one-dimensional (1D) growth of the gel fibrils is mainly governed by the 1D hydrogen-bonded network involving the ion pair. All the non-gelators show either two- (2D) or zero-dimensional (0D) hydrogen-bonded assemblies involving the ion pair. The molecular packing of the fibres in the xerogels of 1, 3, 5 and 6 has also been established on the basis of their simulated powder diffraction patterns, XRPD of bulk solids and xerogels. Ab initio quantum chemical calculations suggests that π–π interactions is not a contributing factor in the gelation process.