We have obtained sorbents modified by the cationic SAS based on hydromica and kaolinite—layer silicates with a rigid structural cell. We have studied structure—sorption properties of initial and developed materials. It has been shown that modification results in a sharp decrease of hydrophilicity of minerals, enhancement of their affinity to the molecules of anionic and nonionogenic SAS. We have noted a substantial increase of sorption capacity of modified minerals with respect to nonionogenic SAS, which is explained by the formation on the surface of the sorbent of bulk associates from the molecules of cationic and nonionogenic SAS.