Poly (4-methyl-2-pentyne) (PMPentyne) and poly (4-methyl-1-pentene) (PMPentene) as membrane gas-separating media were studied with a combination of experimental and theoretical approaches. Experimental approaches included the permeability measurements for C1–C4 alkanes in linear heating mode (for PMPentyne) and under isothermal conditions (for PMPentene), and diffusivity evaluation by a differential method for PMPentene. Theoretical approaches included the ‘hard-spheres’ theory for calculation of gas solubility in PMPentyne and gas transport theory for two-phase systems for the estimation of the amorphous and crystalline phases contribution in PMPentene. Correlation analysis was used for any type of gas transfer parameter calculation where experimental data were lacking. These combinations of methods allowed obtaining the whole set of parameters for any gas–polymer pairing and explained the butane-selective properties revealed in PMPentyne (C1 < C2 < C3 < C4) and methane-selective properties of PMPentene (C1 > C2 > C3 > C4).