A new synthetic route for the preparation of poly(methyl methacrylate)/montmorillonite (PMMA/MMT) nanocomposites was reported. In this method, first 4-(dimethylamino)benzoate group was incorporated into silicate layers of clay by esterification reaction and used to produce PMMA/MMT nanocomposites by in situ Type II photoinitiated free radical polymerization. In situ photopolymerization of methyl methacrylate through into the silicate layers by either visible or UV light irradiation leads to PMMA/MMT nanocomposites. Copyright © 2011 Wiley Periodicals, Inc.