Novel periodic mesostructured organometallic silicas of MCM-41 type bearing homogeneously distributed bis(8-quinolinolato)dioxomolybdenum(VI) inside the channel walls (denoted as MoO(2)Q(2)@PMO-x) are synthesized via a convenient one-pot method and examined as catalysts in the epoxidation of cyclooctene. The ordered mesoporous structures as well as the organometallic groups incorporated into the framework are fully determined by comprehensive characterization techniques such as XRD, TEM, N(2) adsorption/desorption, SEM, FT-IR, UV-vis spectroscopy, solid-state NMR, ICP-AES, XPS and TG/DSC. MoO(2)Q(2)@PMO-6% catalyst exhibits higher activity for the epoxidation of cyclooctene with tert-butyl hydroperoxide than other MoO(2)Q(2)@PMO materials and its homogeneous or randomly grafted analogue. (C) 2011 Elsevier Inc. All rights reserved.