Pd-doped organosilica membranes were prepared by controlling calcination atmospheres (

i.e

. POS-Air

POS-N

2

POS-H

2

POS-H

2

/N

2

) 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 calcination atmosphere is more beneficial to maintain organosilica moieties in POS networks. POS-H

2

/N

2

membrane showed the optimal H

2

separation performance that its permselectivities for H

2

/CO

2

H

2

/N

2

H

2

/CH

4

and H

2

/SF

6

are 15.0

96.7

173.0 and 3400.0

respectively. Moreover

it is found that H

2

molecules pass through the four membranes based on activated diffusion

while CO

2

molecules permeation through POS-N

2

and POS-Air membrane is dominated by surface diffusion. This work may provide insight into the understanding of the calcination atmosphere effect on gas separation performance of metal-doped organosilica membranes.