The hydrothermally stable and long-range ordered Ce-MCM-48 and Fe-MCM-48 were conveniently synthesized at 393 K for 24 h by directly adding fluoride ions to the initial gel without posttreatment and pH adjustment. The Ce-MCM-48 with a Si/Ce of 200 and 100, which were prepared by directly adding fluoride ions, could still maintain their mesoporous structures after refluxing in boiling water for 3 days. The incorporation of Ce into MCM-48 could enhance the hydrothermal stability of MCM-48 in the absence of fluoride ions; however, the incorporation of Fe into MCM-48 materials barely improved the hydrothermal stability of MCM-48 materials. The effect of adding NaF was much more efficient in enhancement of hydrothermal stability than that of the incorporation of Ce. The addition of fluoride ions mainly improves the degree of polymerization of silicates. The Ce(4+) ions in Ce-MCM-48 appear to be present partly in tetrahedral coordination in the framework and partly as CeO(2) particles on the surface of framework. The Ce positioned on the surface of pore walls and in the framework both provide the protection against water attack.