Organo-vermiculites (organo-Vts) were prepared by intercalation of four designed gemini surfactants (BDIN, BDHP, BDPD, BDPB) with different functional groups (imino, hydroxy, phenyl, pyridyl) into vermiculite (Vt). The structures and properties of four obtained organo-Vts were tested by a series of characterization techniques. Rhodamine B (RhB) was chosen as the target contaminant to investigate the impacts of type and location of surfactant functional group on adsorption process. The adsorption of RhB onto organoclays was in the order: BDIN-Vt > BDHP-Vt > BDPD-Vt > BDPB-Vt, especially BDIN-Vt with the maximum adsorption capacity (q(max)) of 528 mg g(-1), which was much larger than known existing adsorbents. Differentiations of the adsorption capacity verify that (i) the combination of hydrogen bond and XH-pi interaction was beyond pi-pi interactions, (ii) pi-pi interactions between the benzene rings surpassed the pi-pi interactions between heteroaromatic ring and benzene ring, (iii) the gemini surfactant with polar spacers in the main chain is more favorable for adsorption than that in the pendant group. The key factors which influence the adsorption process were also explored. Additionally, adsorption kinetics, isotherm and thermodynamic parameters were discussed. The work provides new insight into design of excellent adsorbents with organo-clays to remove organic pollutants.