This paper builds on the preceding researches to study the effects of the type of clays (montmorillonites K10, KSF) and modifying conditions on the structure and adsorption behavior of resulting clay adsorbents. The raw clays were modified by polymeric Al/Fe species, hexadecyl-trimethylammonium (HDTMA) surfactant and a complex of polymeric Al/Fe-HDTMA. X-ray diffraction spectra was applied to analyze the structure of the raw and modified clays. After modification, the basal spacing of the clays varied, depending on the types of raw clay and modification conditions. Copper and phenol were selected as adsorbates for evaluating the adsorption performance of various clays, which was affected significantly by the types of raw clay and modification conditions. In general the inorganic contaminant (e.g., Cu) tend to be adsorbed by the polymeric Al/Fe modified clay and the organic impurities (e.g., phenol) will be preferably captured by the surfactant modified clay; both due to the specific surface properties resulting from introducing the modifiers. The complex modified clays possessed the ability of adsorbing both inorganic and organic contaminants. In addition, the d 0 0 1 spacing of modified KSF was greater than that of K10; the adsorption performance with modified KSF was thus greater than that with the modified K10. Finally, the ratio of modifiers to the clay (metal:surfactant:clay) has been observed to affect the adsorption performance; the optimal conditions have been defined.