Direct hydrothermal synthesis (HT), template ion-exchange (TIE) and molecular dispersion (MD) approaches were used to introduce manganese species into MCM-48-type mesoporous materials. The tungsten was highly dispersed within the channels of mesoporous MnMCM-48 samples by chemical grafting (CG) via a liquid–solid reaction. The prepared manganesosilicate and tungstenomanganesosilicate MCM-48-type mesoporous materials were characterized by physico-chemical techniques, including TEM, N2 sorption, XRD, XPS, UV-Vis and elemental analysis. The physico-chemical characterization revealed that all of the samples retained a high surface area, a regular cubic mesoporosity and that the Mn and W were highly dispersed. The higher unit cell parameter/pore wall thickness values of the MnMCM-48 and WMnMCM-48 samples relative to that of pure MCM-48 indicate the incorporation of Mn and W into the framework/channels of MCM-48. The Mn and W species existed as isolated sites in the framework/extra-framework or as monomolecular species. No bulk manganese or tungsten was observed outside the MCM-48-type mesoporous materials. The coexistence of Mn2+, Mn3+ or/and W6+ was evidenced by XPS and UV-Vis spectroscopic measurements. The catalytic activities of these samples were studied with respect to the conversion of methylcyclopentane (MCP) in reductive media as a function of Mn loading and reaction temperature (200–500 °C). Whatever the manganese content and irrespective of the temperature of reaction, the MnMCM-48 mesoporous samples did not exhibit catalytic activity, which suggests that the electrophilic manganese oxygen species, operative over all the samples, were inactive sites for the conversion of MCP. The addition of tungsten favored catalytic activity. When the WMnMCM-48 was not calcined, only the methane (C1) cracking product was observed to be formed by successive rupture of C–C bonds starting at 400 °C. When the WMnMCM-48 was calcined, ring-opening products formed by the C–C rupture, at substituted and unsubstituted carbon atoms, were observed starting at 400 °C. This behavior is associated with a symbiotic process between the MnMCM-48 support and the W nanoparticles.