With use of 3-aminopropyltrimethoxysilane (APS) and PbCl2 as the organic and inorganic precursors, respectively, a novel layered perovskite-type organic/inorganic derivative containing silica networks intercalated in the inorganic sheets consisting of PbCl4 2- was prepared. This material was observed to show the exciton emission (336 nm) from the PbCl42- inorganic layers and a strong blue emission (438 nm) related to the silica networks.