The catalytic performance of the isomerization of styrene oxide to phenyl acetaldehyde was investigated over different modified beta catalysts under gas-phase atmosphere free of solvents. The physicochemical properties were characterized by a combination of X-ray diffraction (XRD), N-2 adsorption, Fourier transform infrared spectroscopy (FT-IR), Magic Angle Spinning Nuclear Magnetic Resonance (MAS-NMR), NH3-Temperature programmed desorption (NH3-TPD) and thermo gravimetric analysis (TGA), etc. Acid sites with stronger strength are responsible for the formation of condensation products and fast deactivation of catalysts. The obtained results also demonstrate that the introduction of boron atoms can create suitable acid strength and acid distribution without significantly destroying its microporous structures. Therefore, BAl-BEA sample is highly active and selective for the rearrangement of styrene oxide as well as very stable to deactivation.