Methods of estimation of molecular-selective gas transport parameters in polymeric membranes and explanation of separation selectivity evolution for 'small' and 'large' molecules up to inversed selectivity are proposed based on comparative analysis of diffusion and solubility of noble gases as isotropic diffusion probes in different classes of polymers and block copolymers on their basis. Two approaches are considered in this work: (1) analysis of diffusional migration of permanent gases, lower hydrocarbons, and alcohols (vapor) in glassy polymers and rubbers relative to the diffusion of noble gases including radon; (2) adaptation of the 'hard sphere' theory developed for gas solubility in liquids to the calculation of the solubility of gases in the polymer matrix. In the latter case, noble gases as isotropic probes are used for calculating the required fitting parameters of the polymer medium.