Zwitterionic gemini surfactants, 1,2-bis[N-methyl-N-(3-sulfopropyl)-alkylammonium] ethane betaines (alkyl, n = 12, 14, 16), are synthesized and used to modify Na-vermiculite (Na-Vt) into organo-vermiculites (OVts) serving as adsorbents for Congo red (CR). FT-IR, XRD, EA, TG-DTG, SEM and BET are utilized for characterization of OVts. Adsorption factors such as surfactant dosage, contact time, pH, initial concentration and temperature are adopted to batch experiments, which all fit well with pseudo-second kinetic model and Freundlich isotherm model. The results show that the OVts have resistance to pH change, but are greatly affected by temperature. 12–2–12Vt is exothermic sorption process which shows higher efficient CR removal of 807.55 mg g −1 ( C 0 = 1000 mg L −1 ) at 298 K. On the contrary, 14–2–14Vt and 16–2–16Vt are endothermic sorption processes exhibiting superior uptake amounts as 1682.76 mg g −1 and 1644.78 mg g −1 ( C 0 = 2000 mg L −1 ) at 328 K, respectively. Combining the results of thermodynamic data, log K om values, frontier orbital simulations and ECT (electrophilicity charge transfer) values as well as characterization of spent OVts, it can be concluded that (i) The functional groups (SO 3 - ) of modifiers which are the HOMO orbitals serve as electron-donor and promote the CR adsorption. (ii) The two long alkyl chains form hydrophobic interaction and favor the CR removal. The OVts show efficient adsorptive capacities implying that zwitterionic gemini surfactants are well desirable for modification of Na-Vt for removal of CR from wastewater. • Zwitterionic gemini surfactants are applied to modify vermiculite for CR removal. • Efficient adsorption of CR is achieved on 14–2–14Vt at 328 K (1682.76 mg g –1 ). • The adsorption capacity of OVts is stable with the change of pH in 5–9. • Adsorption mechanism is revealed by characterization, experiment and calculation.