Abstract: The electron spin resonance (ESR) technique has been used to study the motion and segregation of an organic spin probe cation (4-amino-2,2,6,6-tetramethylpiperidine N-oxide) on K+-hectorite as a function of average surface concentration. The organic cation tends to concentrate in certain interlayers of aqueous hectorite suspensions even when it occupies a small fraction of the cation-exchange sites. This demixing effect is not evident in methanol-solvated hectorite. The average mobility of the probe increases at higher adsorption levels as a result of the shift of the equilibrium in favor of the solution state. Calculated time-averaged orientations of the probe on the clay surfaces are quite different for methanol- and water-solvated systems, emphasizing the importance of the solvent in modifying the surface-cation interaction.