Adding organically modified bentonite into impervious wall materials may improve the adsorption of organic pollutants. In this study, cetyltrimethylammonium bromide organically modified bentonite (CTMAB bentonite) was mixed with sodium bentonite and kaolin to obtain two materials, which were then used as cut-off walls for typical pollutants. Soil column consolidation tests, diffusion tests, and breakdown tests were conducted to study migration of organic pollutants in soil columns. The parameter sensitivity of pollutant transport in the cut-off wall was analysed by numerical simulation. The sodium bentonite mixed with 10% CTMAB bentonite and kaolin-CTMAB bentonite showed the greatest impermeability: with a consolidation pressure of 200 kPa, the permeability coefficients were 1.03 × 10⁻⁸ m/s and 3.49 × 10⁻⁹ m/s, respectively. The quantity of phenol adsorbed on sodium bentonite-CTMAB bentonite increased with increasing water head height. The kaolin-CTMAB bentonite column showed the best rhodamine B adsorption performance, and the adsorption rate reached 98.9% on day 67. The numerical results showed that the permeability coefficient was positively correlated with the diffusion of pollutants in the soil column. The quantity adsorbed on the soil column was positively correlated with the retardation factor, and the extent of pollutant diffusion was negatively correlated with the retardation factor. This study provides a technical means for the optimal design of organic pollutant cut-off walls.