Zeolite membranes can be used as vapor separation membranes due to the adsorption properties of zeolite crystals. Recently, vapor separation membranes are paid attention in the petrochemical complexes by combining with distillation separation methods. Heat duty for separation can be reduced by the combination of distillation and membrane. Zeolite membranes are usually crystalized on porous ceramic substrates such as a porous alumina substrates. Here, we had paid attention to novel porous silica substrates. In this study, effects of porous silica substrates on preparation of MFI zeolite membranes were investigated to obtain high permselective membranes. Acetic acid vapor permeation tests were conducted for the typical application in the petrochemical complexes. Porous silica (pore size: 500 nm) or porous α-alumina (pore size: 700 nm) were used as ceramic substrates. The seed crystals were coated by changing the seed slurry (0.5g L-1) of pH from 2 to 12. MFI membranes were crystalized at 180 °C for 16 h. The parent gel compositions for the membranes synthesis were SiO2: TPABr: Na2O: H2O=1: 0.2: 0.04: 600 (mol/mol). Vapor permeation tests of acetic acid/water were carried out at 110 °C. N2 permeance through the membrane prepared on the silica substrate was 3.6 × 10-6 mol m-2 s-1 Pa-1, while that through the membrane prepared on the alumina substrate was only 1.4 × 10-6 mol m-2 s-1 Pa-1. The initial resistance through the alumina substrate was lower than that through the silica substrate. This shows that the effective MFI layer was thinner on the silica substrate. N2 permeances through all the membranes were similar at around 4 × 10-6 mol m-2 s-1 Pa-1. The maximum N2/SF6 permeance ratio was 79.3 through the membrane coated at pH 2. Thus, seed coating was important to obtain high gas permselective membranes. The separation factor of acetic acid through the MFI membrane was over 20. Thus, we have concluded the MFI membrane was acetic acid permselective membrane.