Free volume in a big group of glassy polymers distinguished by a wide range of gas permeability (P in the range 1−104 Barrer) was studied using the positron annihilation lifetime (PAL) method. To take into account an additional channel of decay of positronium (Ps), caused by the reaction with sorbed O2, measurements were performed both under ambient conditions and under a nitrogen atmosphere. The finite-term and continuous lifetime analyses (PATFIT and CONTIN programs) were used for the treatment of the positron annihilation decay curves. It was shown that better statistical fitting parameters can be obtained for four component PAL spectra of a vast majority of the glassy polymers studied. The presence of two Ps lifetimes (τ3 = 1.7−3.3 ns and τ4 = 2.7−10.9 ns) indicates that size distribution of free volume elements (FVE) in glassy polymers is typically bimodal. The presence of smaller and larger FVE (R3 = 2.5−3.5 A, R4 = 3.5−7.0 A) was proved by PATFIT analysis of the data. Continuous analysis clearly in...