The adsorption of dodecyltrimethylammonium (DTA +) and cetyltrimethylammonium (CTA +) ions together with that of the Br − counterions on two types of silica has been measured as a function of the pH of the aqueous solution. At pH 8 and 9 the DTA + adsorption isotherms show a two-step character. Br − adsorption does not set in before the DTA + adsorption starts to increase to the second plateau. At pH 10, the DTA + adsorption continuously increases to one final plateau value, but again Br − only starts to be adsorbed once a certain minimum concentration is exceeded. For CTA + the isotherms are single-step at all three pH values, but the Br − isotherms are similar to those in the DTA + system. When the aqueous solutions are 1 M in n-butanol, the maximum DTA + adsorption is restricted to the value of the mentioned first plateau, while CTA + adsorption at maximum is also limited to about half the value it reaches in the absence of butanol. In 1 M butanol, Br − adsorption no longer takes place. The adsorption of cationic surfactants has been supplemented by electrophoresis measurements under the various conditions and by determination of the critical micelle concentrations of the two surfactants in aqueous n-butanol solutions. The results support a model proposed by Rupprecht, according to which at low surfactant concentrations a monolayer is formed, due to interaction of opposite charges on the silica surface and the surfactant ions. At higher concentrations a different mechanism (probably hydrophobic bonding) causes a bilayer to be built up. Application of this model allows the number of dissociated and undissociated silanol groups on the silica surface to be determined as a function of the pH. The calculated pK-value for surface silanol groups appears to be somewhat lower than hitherto assumed.