Catalytic nickelsilicate membranes were synthesized by in-situ techniques on pretreated α- and γ- alumina supports. The resulting films and bulk materials have been characterized by XRD, N2 adsorption-desorption, SEM, TEM and FTIR spectroscopy. Their permeation performances of gases and liquids and catalytic activity in the selective oxidation of styrene with H2O2 have been evaluated. The formation, morphology, permeation and catalytic properties of the membranes have been correlated with nature of alumina supports, their surface pretreatment and conditions of the hydrothermal synthesis. The results show a strong effect of γ-alumina surface on the morphology and properties of the membranes.