The reactivity of synthetic expandable fluorine micas [MxMg3-xLix(Si4O10)F-2 (M = Li, Na, K), x = 0.4, 0.5, 0.6, 0.8] with titania sol was investigated. The interlayer cation species of host micas have a strong effect on the complex formation, resulting in different titania contents and surface areas of titania-pillared micas in the order K+ < Na+ < Li+. This is due to the difference in the expandability of host micas. The layer charge (x) also affects the complex formation. The Na-x-series gave a maximum of titania content at x = 0.6.