Here, reduced graphene oxide (r-GO) nanosheets were embedded in an organosilica network to assemble an ultrathin hybrid membrane on the tubular ceramic substrate. With the organosilica nanocompartments inside the r-GO stacks and the intensified polymerization, r-GO sheets endow the as-prepared hybrid membranes with high H(2) and CO(2) separation performance. The resulting selectivities of H(2)/CH(4) and CO(2)/CH(4) are found to be 223 and 55, respectively, together with gas permeance of approximately 2.5 × 10(-7) mol·m(-2)·s(-1)·Pa(-1) for H(2) and 6.1 × 10(-8) mol·m(-2)·s(-1)·Pa(-1) for CO(2) at room temperature and 0.2 MPa. To separate larger molecules from H(2), the H(2)/C(3)H(8) and H(2)/i-C(4)H(10) selectivities are as high as 1775 and 2548, respectively. Moreover, at 150 °C and 0.2 MPa, the hybrid membrane retains high separation performances with ideal selectivities higher than 200 and 30 for H(2)/CH(4) and CO(2)/CH(4), respectively, which are attractive for gas separation and purification of practical applications.