Polysiloxane-immobilized monoamine, diamine, and triamine ligand systems of the general formula P-(CH2)(3)-X [where P represents a polysiloxane three-dimension silica like network, and X represents monoamine(-NH2), diamine (-NH(CH2)(2)NH2), or triamine (-NH(CH2)(2)NH(CH2)(2)NH2) functional ligand groups] were prepared by hydrolytic polycondensation of the tetraethylorthosilicate (TEOS) and the appropriate amine silane coupling agent (RO)(3)Si-(CH2)(3)X in the presence of cetyltrimethylammonium bromide (CTAB) as surfactant using the sol-gel method. The polysiloxane-immobilized amine ligand systems exhibit a higher potential for divalent metal ions (Cu2+, Ni2+, Co2+) when CTAB was used as surfactant than those of the corresponding polysiloxane ligand systems prepared without CTAB. X-ray Photoelectron Spectroscopy (XPS) analyses show a significant change in the surface composition as resulting from the incorporation of CTAB, which can be related to the increase in the uptake of metal ions.