TiO₂-pillared clays with well-ordered porous structures are successfully prepared via incorporating TiO₂ nanosol particles into the clays, where empty octahedral sites are partially modified with divalent metal ions such as Mg²⁺ and Fe²⁺. The prepared TiO₂-pillared mica exhibits excellent photocatalytic activity, which can be controlled by tuning the optical transparency of clay support rather than the specific surface area of the hybrid catalysts.