Stable alginate microcapsules in dried form containing bis(2,4,4-trimethylpentyl) monothiophosphinic acid (HA) were prepared by coating of fresh alginate microcapsules with chitosan or polyethyleneimine (PEI). The thickness of coatings was estimated by electron probe microanalysis (EPMA), along with electron microscopy (SEM), as well as comparison of uptake percentage of coated and uncoated hollow capsules. Characterization of microcapsules was carried out by Ag+ uptake experiments, destructive chemical analyses and thermogravimetric methods (TG and DTA). Chemical stability tests in HNO3 and NaNO3 media indicated that the coating with 4-double layer chitosan or mono-layer PEI led to an appreciable enhancement of impermeability in the range of pH > 1 or [Na+]< 1M (mold m(-3)). Unfortunately, multiple coating causes some extractant losses due to effect of physical stress during the coating; however, PEI-coated microcapsules nearly completely hold their extractant content. Stable extractive microcapsules have an appreciable potential for the selective removal of heavy metal ions.