An oriented submicron silicalite membrane has been prepared by growing a layer of oriented silicalite crystals on a composite precursor nanocrystalline silicalite/alumina film using controlled secondary growth. The orientation of the crystals at the surface was such that both straight and sinusoidal channel networks run nearly parallel to the membrane surface. The membrane exhibits ideal selectivities for H2 over N2 as high as 60 at 150°C and O2 over N2 as high as 3.6 at 185°C. H2, N2 and O2 permeances are 2.13, 0.05 and 0.17 cm3 (STP)/(cm2·min·atm) at 185°C, respectively, and the corresponding apparent activation energies are 11, 26 and 32 kJ/mol. The permeation characteristics are attributed to the preferred orientation of the molecular sieving layer.