As the field of anion exchange membranes (AEMs) employs an increasing variety of cations, a critical understanding of cation properties must be obtained, especially as they relate to membrane ion conductivity. Here, to elucidate such properties, metal cation-based AEMs, featuring bis(norbornene) nickel, ruthenium, or cobalt complexes, were synthesized and characterized. In addition, isothermal titration calorimetry (ITC) was used to probe counterion exchange thermodynamics in order to understand previously reported differences in conductivity. The ion conductivity data reported here further demonstrated that nickel-complex cations had higher conductivity as compared to their ruthenium and cobalt counterparts. Surprisingly, bulk hydration number, ion concentration, ion exchange capacity, and activation energy were not sufficient to explain differences in conductivity, so the thermodynamics of metal cation-counterion association were explored using ITC. Specifically, for the nickel cation as compared to the other two metal-based cations, a larger thermodynamic driving force for chloride counterion release was observed, shown through a smaller Δ Htot for counterion exchange, which indicated weaker cation-counterion association. The use of ITC to study cation-counterion association was further exemplified by characterizing more traditional AEM cations, such as quaternary ammoniums and an imidazolium cation, which demonstrated small variances in their enthalpic response, but an overall Δ Htot similar to that of the nickel-based cation. The cation hydration, rather than its hydration shell or the bulk hydration of the membrane, likely played the key role in determining the strength of the initial cation-counterion pair. This report identifies for the first time how ITC can be used to experimentally determine thermodynamic quantities that are key parameters for understanding and predicting conductivity in AEMs.