The relative affinity of the monovalent metal ions Li, Na, Cu and Ag towards a series of aliphatic alkyl acetates and some selected 1-alkenes (P) was examined using the kinetic method. A detailed analysis of the dissociation characteristics of a series of mixed metal-bound dimer ions of the type P-M-P and the evaluated proton affinities (PAs) of the monomers shows that the affinity of the cation towards long-chain alkyl acetates and alkenes (having a chain length ≤ C) is markedly enhanced. In line with recent studies of nitriles, alcohols and methyl alkanoates, this is attributed to a bidentate interaction of the metal ion with the functional group or double bond and the aliphatic chain. In particular, the longer chain alkyl acetates, methyl alkanoates and alcohols show a remarkably similar behaviour with respect to silver ion hydrocarbon bonding. The Ag adducts of the alkyl acetates dissociate by loss of CHCOOH. This reaction becomes more pronounced at longer chain lengths, which points to metal ion bidentate formation in [Ag···1-alkene] product ions having a long hydrocarbon chain. In the same vein, the heterodimers [1- hexene···Ag···1-heptene] and [1- heptene···Ag···1-octene] dissociate primarily into [Ag···1-heptene] and [Ag···1-octene] ions, respectively. Hydrocarbon bidentate formation in [Ag···1-octene] also reveals itself by the reluctance of this ion to react with water in an ion trap, as opposed to [Ag···1-hexene] which readily undergoes hydration.