Relative affinity measurements of monovalent metal ions (=Li+, Cu+ and Ag+) towards aliphatic amines, alcohols and methyl alkanoates (P) have been performed using the kinetic method on the dissociation of metal-bound dimer ions of the type P1–M+–P2. It was found that the cations' affinity towards long chain (≥C4 chain length) n- and s-alkylamines, n-alkanols and methyl n-alkanoates was unexpectedly enhanced. This is attributed to a bidentate interaction of the metal ion with the amine, alcohol or ester functional group and the aliphatic chain, paralleling earlier observations on metal-bound nitriles. Methyl substitution at the functional group ( s-alkylamines compared with n-alkylamines) serves to strengthen only the N M+ bond, and this can be rationalised by the larger proton affinities of s-alkylamines compared to n-alkylamines. This substitution, however, has no effect on the metal ion–hydrocarbon bond. In contrast, methyl substitution remote from the functional group, as in iso-pentylamine, does lead to strengthening of the metal ion–hydrocarbon bond. The cuprous ion affinity of hexadecylamine, C16H33NH2, was found to be as large as that for ethylenediamine (352 kJ mol−1), known to be a strong copper binding agent. It is argued that such a metal ion - hydrocarbon interaction does not occur in the metal bound dimers.