A series of molybdate-intercalated and stabilized magnesium‐iron hydrotalcite (HMFeMo) materials with different molybdate loadings were successfully prepared by an in-situ hydrothermal method. The prepared HMFeMo materials were systematically characterized using Fourier-transform infrared spectroscopy (FT-IR), powder X-ray diffraction (XRD), Ultraviolet-visible spectroscopy, scanning electron microscopy, thermo-gravimetric analysis, nitrogen adsorption-desorption and X-ray photoelectron spectroscopy (XPS) experiments. The XRD results demonstrated the successful intercalation of molybdate ions in the interlayer space of magnesium-iron hydrotalcite and the stabilization of the layered structure. In addition, the XPS spectra of the HMFeMo materials revealed the presence of molybdenum in a higher-valent oxidation state. The calcination of HMFeMo materials led to the formation of solid solution of mixed metal oxides. Both the as-prepared and calcined HMFeMo catalysts showed promising activity for the epoxidation of cyclooctene, as a model reaction. Furthermore, the performance of the as-prepared and calcined HMFeMo catalysts for the oxidation of a biomass model compound, namely isoeugenol to vanillin, was evaluated. The isoeugenol conversion over the as-prepared HMFeMo catalysts under solvent-free conditions and using tertiary-butyl hydroperoxide in decane as the oxidant was good. Moreover, the isoeugenol conversion and selectivity toward vanillin of HMFeMo0.1, with a molybdate loading of 0.1 mol %, were the highest (86.2% and 83.1%, respectively) of all HMFeMo catalysts in this study at 80 °C for 5 hr. HMFeMo0.1 presented the best catalytic activity for both the epoxidation of cyclooctene and oxidation of isoeugenol to vanillin, and its activity remained unchanged after several runs.