Selective cation exchange for Cu and Pb has been demonstrated with the high-charge-density sodium fluorophlogopite mica, Na-4-mica. The 2Na(+) --> M2+ exchange reaction (M = Cu or Pb) was investigated with Na-4-micas prepared by two different synthetic processes. One was easily and economically prepared by crystallization from a mixture of NaF, MgO, and metakaolin, the latter serves as an inexpensive aluminosilicate source. Another was prepared by solution-sol-gel processing. Ion-exchange isotherms for Cu2+ and Pb2+ were obtained at room temperature. The thermodynamic functions for the initial ion-exchange reactions were calculated because the isotherms were not completed. High selectivities for both copper and lead exchange were found on the highly crystallized Na-4-mica prepared from metakaolin. Their ion-exchange capacities were 225 and 257 milliequivalents per 100 g of dry clay for Cu2+ and Pb2+, respectively. This high level decontamination of copper and lead with the highly crystallized Na-4-mica from metakaolin will be a very important separation required for purification of drinking water as well as for wastewater treatment and disposal.