Abstract: Ganophyllite and [Na⁺ + Al³⁺]-substituted tobermorite exhibited similar cation exchange properties and, in particular, selective cesium exchange. [Na⁺ + Al³⁺]-substituted tobermorite and ganophyllite showed a selective Cs exchange of 10.77 and 8.71 meq/100 g from 0.02N NaCl and of 11.08 and 9.04 meq/100 g from 0.02N CaCl₂, respectively. The [Na⁺ + Al³⁺]-substituted tobermorite is structurally similar to ganophyllite: both are roughly analogous to 2:1 layer silicates, both have cross-linking tetrahedra across the interlayer region, and both have exchangeable cations located in zeolite-like sites in the interlayer region. The similarities in cation exchange properties imply that the residual charge configuration of the analogue 2 : 1 layer must be approximately equivalent also.