There is a need to develop highly CU2+ selective materials which can potentially remediate copper contaminated soils and water. Here we show that several highly charged synthetic swelling mica-type clays are highly selective for copper exchange. The synthetic micas have cation exchange capacities (CECs), which are close to their theoretical values. Both Na-saturated and Mg-saturated micas were investigated for Cu ion exchange selectivity. Ion exchange isotherms and Kielland plots were constructed using the equilibrated solution analyses. From these studies it was found that Na-4-mica and Na-3-mica could selectively exchange copper at lower concentrations from solution, whereas Na-2-mica sample performed better by showing Cu ion exchange selectively to almost its capacity. The EPR spectra of Cu-exchanged micas coincide with the mica's charge characteristics that predict increased binding strength of exchangeable Cu in Na-4-mica and Na-3-mica than in Na-2-mica.