Abstract: Boron adsorption on 2-0.2-µm size fractions of kaolinite at 25° ± 2°C at pH values between 6.0 and 10.5 was studied. The kaolinite sample was pretreated to remove any surface oxide and hydroxide coatings. The initial concentrations of boron in solution ranged between 2 and 10 mg/liter with either KClO4 or Ca(ClO4)2 as background electrolyte at constant ionic strength of 0.09 ± 0.01 mole/liter. Boron speciation in equilibrium solutions was calculated by using the chemical equilibrium computer program GEOCHEM. The adsorption of boron on kaolinite in either medium showed similar dependence on pH and initial boron concentrations. Boron adsorption at higher pHs was noticeably higher in Ca(ClO4)2 medium as compared to KClO4 medium. These differences were attributed to the formation and adsorption of CaB(OH4)+ ion-pair species.