The binding of calcium and magnesium ions (M2+) by polymers and other macromolecules in aqueous solution is ubiquitous across chemistry and biology. At present, it is difficult to assess the binding affinity of macromolecules for M2+ without recourse to potentiometric titrations and/or isothermal titration calorimetry. Both of these techniques require specialized equipment, and the measurements can be difficult to perform and interpret. Here, we present a new method based on 1H NMR chemical shift imaging (CSI) that enables the binding affinity of polymers to be assessed in a single experiment on standard high-field NMR equipment. In our method, M2+ acetate salt is weighed into a standard 5 mm NMR tube and a solution of polymer layered on top. Dissolution and diffusion of the salt carry the M2+ and acetate ions up through the solution. The concentrations of acetate, [Ac], and free (unbound) M2+, [M2+]f, are measured at different positions along the sample by CSI. Binding of M2+ to the polymer reduces [M2+]f and hinders the upward diffusion of M2+. A discrepancy is thus observed between [Ac] and [M2+]f from which the binding affinity of the polymer can be assessed. For systems which form insoluble complexes with M2+, such as sodium polyacrylate or carboxylate-functionalized nanocellulose (CNC), we can determine the concentration of M2+ at which the polymer will precipitate. We can also predict [M2+]f when a solution of polymer is mixed homogeneously with M2+ salt. We assess the binding properties of sodium polyacrylate, alginate, polystyrene sulfonate, CNC, polyethyleneimine, ethylenediamenetetraacetic acid, and maleate.