A hydrogen-selective and hydrothermally stable membrane composed of silica-zirconia layer deposited on a modified alumina sub layer was successfully prepared. The composite membrane was used for hydrogen purification from synthesis gas in steam methane reforming process. Silica-zirconia layer was synthesized using the CVD method at 923K and atmospheric pressure while the alumina base layer was prepared via sol-gel procedure. DLS, XRD, SEM/EDX, and BET characterization techniques were used to prove that gamma-alumina base and silica-zirconia layer are fabricated successfully. Using the composite membrane, hydrogen selectivity toward other gases has improved significantly. Moreover, H-2/CH4, H-2/CO, and H-2/CO2 selectivity have been increased from 700, 350 and 70 in 5 h CVD synthesized membrane to 1600, 750 and 570 for 12 h CVD synthesized membrane respectively. The synthesized Silica-Zirconia membrane successfully altered gases permeability tendency order from H-2 > CH4 > CO2 > CO to H-2 > CO2 > CO > CH4 which leads to better separation of the product from methane feed. Finally, hydrothermal stability test demonstrated that permeability loss in silica-zirconia CVD coated membrane for H-2 is 45.7% after 48 h, while for silica CVD coated on the modified alumina approaches 92.5%. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.