Abstract: The exchange of Rh(NBD)(Pφ3)2+, Rh(NBD)(PMe2φ)3+, Rh(COD)(Pφ3)2+, and Rh(PMe2φ)4+ on hectorite was studied in methanol/dichloromethane, acetone, dimethylformamide, and acetonitrile. At low initial Rh+ concentration and short contact times, ion exchange was the predominant process, and its selectivity and maximum capacity were solvent-dependent. High initial Rh+ concentrations, long contact times, and the most polar solvents favored intersalation and salt precipitation. In all experiments monolayers of complex formed in the interlamellar space and were very tightly held. The complexes retained their integrity on the surface even after removal of all solvent molecules.