We report insertion of Ag atoms into layered MoO3 via an in situ template route. PVP-Ag+ complex self-assembled with inorganic (MoxOy)(infinity)(n-) chains into a layered hybrid, in which the PVP-Ag complex was intercalated between the (MoxOy)(infinity)(n-) layers. Calcinations of this hybrid at 500 degrees C lead to formation of Ag/MoO3 hybrid, in which Ag nanoparticles of about 1 nm have been inserted between the MoO3 layers. By this method pillared MoO3 has been obtained very easily. We believe that this research opens new routes to fabricate novel intercalation compounds and metal/semiconductor nanohybrids via an efficient and green route. Crown Copyright (c) 2012 Published by Elsevier Ltd. All rights reserved.