Pd-doped organosilica membranes were prepared by controlling calcination atmospheres (i.e. POS-Air, POS-N2, POS-H2, POS-H2/N2) to tailor their networks for improving their gas separation performance. This study shows that Pd (II) could be only maintained under non-reductive calcination atmosphere, while inert and reducing cal-cination atmosphere is more beneficial to maintain organosilica moieties in POS networks. POS-H2/N2 membrane showed the optimal H2 separation performance that its permselectivities for H2/CO2, H2/N2, H2/CH4 and H2/SF6 are 15.0, 96.7, 173.0 and 3400.0, respectively. Moreover, it is found that H2 molecules pass through the four mem-branes based on activated diffusion, while CO2 molecules permeation through POS-N2 and POS-Air membrane is dominated by surface diffusion. This work may provide insight into the understanding of the calcination atmo-sphere effect on gas separation performance of metal-doped organosilica membranes.