A metal-template/metal-exchange method was used to imprint covalently attached bis(8-quinolinolato)dioxomolybdenum(VI) and dioxotungsten(VI) complexes onto large surface-area, mesoporous SBA-15 silica to obtain discrete (MoO2T)-T-VI and (WO2T)-T-VI catalysts bearing different metal loadings, respectively. Homogeneous counterparts, (MoO2N)-N-VI and (WO2N)-N-VI, as well as randomly ligand-grafted heterogeneous analogues, MoO(2)(VI)G and WO(2)(VI)G, were also prepared for comparison. X-ray absorption fine structure (XAFS), pair distribution function (PDF) and UV-vis data demonstrate that (MoO2T)-T-VI and (WO2T)-T-VI adopt a more solution-like bis(8-quinolinol) coordination environment than MoO(2)(VI)G and WO(2)(VI)G, respectively. Correspondingly, the templated Mo-VI and W-VI catalysts show superior performances to their randomly grafted counterparts and neat analogues in the epoxidation of cyclooctene. It is found that the representative (MoO2T)-T-VI-10% catalyst can be recycled up to five times without significant loss of reactivity, and heterogeneity test confirms the high stability of (MoO2T)-T-VI-10% catalyst against leaching of active species into solution. The homogeneity of the discrete bis(8-quinolinol) metal spheres templated on SBA-15 should be responsible for the superior performances. (C) 2014 Elsevier B.V. All rights reserved.