Mesoporous molecular sieves MCM-41 modified by single (Ti) and bimetal (Ti-V) ions with highly ordered hexagonal arrangement of their cylindrical channels were prepared by direct synthesis under microwave–hydrothermal (M–H) conditions at 403K. Characterizations with powder X-ray diffraction (XRD), 29Si magic-angle spinning (MAS) NMR, N2 adsorption–desorption, Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), X-ray photoelcctron spectra(XPS) and transmission electron microscopy (TEM) showed that Ti and V ions were introduced into MCM-41 under M-H conditions and Ti/V-Si bond was formed. Results revealed that all the samples were of a typical hexagonal arrangement of mesoporous structure. The modified materials were high active and selective in the epoxidation of styrene at 343 K in comparison with single-functional MCM-41. Moreover, compared to conventional method, the presented microwave hydrothermal synthesis of molecular sieves greatly improved the selectivity to styrene oxide, e.g., it reached 58.6% at styrene conversion of 18.7% over Ti-V-MCM-41 (50).