Thin pure-silica chabazite (Si-CHA) membranes have been synthesized by using a secondary growth method on a porous silica substrate. A CO2 permeance of 2.62 × 10−6 mol m−2 s−1 Pa−1 with a CO2/CH4 permeance ratio of 62 was obtained through a Si-CHA membrane crystallized for 8 h using a parent gel of H2O/SiO2 ratio of 4.6. The CO2 permeance through the Si-CHA membrane on a porous silica substrate was twice as high as that through the membrane synthesized on a porous alumina substrate, which displayed a similar zeolite layer thickness.