A series of titanium silicalite zeolite catalysts were successfully incorporated inside a Pd membrane reactor aiming to improve the direct hydroxylation of benzene to phenol. The correlation between the membrane structure and the reaction efficiency was investigated. The influences of reactor configuration, feed mode, and catalysts on benzene conversion, product yield, hydrogen conversion, and water production rate were examined in detail. The reaction was very sensitive to the porosity of Ti-containing zeolite film and the bonding state of the titanium atom in the titanosilicates (i.e., framework and extraframework titanium). The framework titanium could adsorb active oxygen species to form Ti peroxo species which would suppress the decomposition, while the extraframework titanium promoted the decomposition of active oxygen species leading to more water production. Large inter- and intracrystalline pores as well as mesopores provided the reactive species greater opportunity to contact directly with frame...