The sorption behavior of neptunium on bentonite was studied with batch type sorption and desorption experiments over a pH range of 2 to 8. A series of parallel studies using Na-smectite, Ca-smectite and admixtures of Na-smectite and calcite quantified the capacity of Ca2+ (which occurs in bentonite as an exchangeable cation of smectite and as a component of calcite) to inhibit the sorption of neptunium. The distribution coefficient (Kd) of neptunium for bentonite was constant from pH 2 to 7, while for pure Na-smectite Kd increased below pH 5 due to “specific sorption” of neptunium on Na-smectite. Specific sorption was defined as occurring when neptunium could be desorbed by a strong acid (1 M HCl) but was stable in the presence of 1 M KCl. It was found that the quantity of neptunium sorbed on Na-smectite was inversely proportional to the concentration of Ca2+ in solution, an effect most pronounced at pH <5. These results show that Ca2+ limits the specific sorption capacity of Na-smectite for neptunium. Similarly, in the mixture of Na-smectite and calcite, sufficient Ca2+ was solubilized to depress neptunium sorption. This investigation demonstrates that Ca2+ contained in bentonite as exchangeable cation and released from calcite reduces the specific sorption of neptunium.