The alkylation of phenol with cyclohexanone has been investigated in the presence of a variety of metal cation-exchanged montmorillonites (Mn+-monts; Mn+ = Zr4+, Al3+, Fe3+, Na+) and montmorillonite K10. Al3+-mont is revealed to be an effective catalyst for alkylation of phenol with ketones, Al3+-mont-catalyzed alkylation of phenol with 4-substituted-cyclohexanones produces almost solely trans-(4-alkylcyclohexyl)phenols, which are good starting materials for some liquid crystals. On the other hand, when a similar reaction is carried out with 1-naphthol instead of phenol in chlorobenzene as solvent, the products are tetrahydrobenzonaphthofuran derivatives and 2-(4-alkylcyclohexyl)-1-naphthols, the former being the major and Fe3+-mont being the most effective catalyst.