Pillared clays（Ti-PILCs）were synthesized from Na-type montmorillonite through intercalation with polymeric hydroxy-titanium.The mechanism of the pillaring course was studied by means of magic angle spinning nuclear magnetic resonance（MAS NMR）and diffuse reflectance infrared spectroscopy（DRIFTS）techniques.DRIFTS suggested that after Ti-pillaring，the silicon-oxygen tetrahedral Si—O—Si bond and aluminum oxide octahedral Si—O—Al bond were broken.Meanwhile，NMR also showed the change of the silicon-oxygen tetrahedral structure and aluminum oxide octahedral structure in the pillared clay.In the pillaring process，the titanium hydroxy-oligomeric cations entered the layers of the montmorillonite by ion-exchange，the Si—O—Al bond of the raw clays were broken，the silicon-oxygen tetrahedron structure were overturned，and the reactive oxygen species（structural hydroxyl）reacted with titanium hydroxy-oligomeric cations to form Si—O—M bond.This led to the incorporation of pillaring species of Ti in the layers of the clay.After further heat treatment，the TiO2 pillars were formed in the layers to obtain Ti-PILCs.