Abstract: A hierarchical double-imprinting concept was applied to the preparation of a new organic-inorganic hybrid sorbent for selective separation of Cd(II) from aqueous solution. In the prepared hierarchically imprinted sorbent, both Cd(II) and surfactant micelles (cetylbrimethylammonium bromide) were used as templates. The sorbent was prepared through self-hydrolysis, self-condensation, and co-condensation of the cross-linking agent (tetraethoxy-silicate) and the functional precursor (3- (2-aminoethyl-amino)-propyltrimethoxysilane) in an alkaline media followed by gelation. The selectivity of the sorbent was investigated by a batch competitive ion-binding experiment using an aqueous Cd(II) and Zn(II) mixture. The largest selectivity coefficient for Cd(II) in the presence of Zn(II) was found to be over 100; the largest relative selectivity coefficient between Cd(II) and Zn(II), over 200. The uptake capacity of the prepared hierarchically imprinted sol-gel sorbent and the selectivity coefficient are much higher than those of the sorbent prepared in the absence of CTAB-template. The sorbent possesses a fast kinetics for the removal of Cd(II) from aqueous solution