Highly ordered W-MCM-48 mesoporous materials containing isolated W atoms in tetrahedral framework positions were successfully synthesized following the S+I- pathway, up to a Si/W of 40. When tungsten content was increased up to a Si/W of 20, the ordered cubic structure was only partially maintained, and for a Si/W of 10 an amorphous phase was obtained. Highly isolated tetrahedral framework tungsten atoms in the W-MCM-48 with a Si/W of 40, have been identified by UV-vis band at 225 nm, IR-TF band at 970cm(-1) and XRD. The W 4f XPS results suggest that the tungsten atoms exist in two oxidation states, W4+ and W5+. The morphology of the samples varies as a function of tungsten content. The W-MCM-48 samples with a Si/W ratio of 40 existed as crystals with a unique crystalline morphology consisting of cubes truncated rhombic dodecahedrons belonging to the cubic Ia3d space group, while the samples with a Si/W ratio of 20 exhibited a different morphology consisting of spheres and cubes truncated by rhombic dodecahedrons. A comparison of samples with Si/W of infinity, Si/W of 40 and Si/W of 20 was performed using the conversion of MCP carried out at 450 degrees C under H-2. (C) 2010 Elsevier B. V. All rights reserved.