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[Display omitted] • Two soluble semi-alicyclic homopolyimides with kink structures were synthesized. • Homopolyimides were blended with various ratios and fabricated into dense membranes. • The homo- and blended polyimide membranes showed good gas separation performance. Aromatic polyimides are promising membrane materials for gas separation due to their excellent gas separation properties. Herein, two soluble semi-alicyclic polyimides were synthesized via a one-step thermal imidization process with two semi-alicyclic dianhydrides possessing kink structures: bicyclo[2,2,2] oct-7ene-2,3,5,6-tetracarboxylic dianhydride (BCDA) and 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (DOCDA), and a flexible aromatic diamine: 4,4′-Oxydianiline (ODA). Their homo- and blended membranes were prepared in various mixing ratios (100/0, 75/25, 50/50, 25/75, and 0/100) and their gas permeation properties were investigated for five gases (H 2 , CO 2 , O 2 , N 2 , and CH 4) and selectivity for five gas pairs (H 2 /CH 4 , H 2 /N 2 , CO 2 /CH 4 , CO 2 /N 2 , and O 2 /N 2). The homopolyimides (BCDA-ODA, DOCDA-ODA) exhibited amorphous structure without crystallinity and good solubilities in the casting solvents. BCDA-ODA showed larger d-spacing/FFV values, higher gas diffusivities/gas solubilities than DOCDA-ODA, resulted in higher gas permeabilities and lower gas selectivity, which were remarkably affected by feed temperature. Also, the gas permeability and selectivity of the blended membranes were dependent upon the BCDA/DOCDA mole ratio. The good gas separation performances of homo- and blended membranes were observed for H 2 /CH 4 , H 2 /N 2 , CO 2 /CH 4 , and O 2 /N 2 , which are comparable to those of commercial membrane materials such as P84®, PSF, CA, Matrimid®, etc. [ABSTRACT FROM AUTHOR]