[en] It is well recognized that positron annihilation lifetime (PAL) spectra in polymers have a long-lived component that can be ascribed to ortho-positronium (o-Ps). The lifetime, τ₃, is considered to be a measure of the size of the micro-vacancies in which o-Ps is trapped and is annihilated through pick-off annihilation with the rate which depends on the size of the vacancy. Positron lifetime measurements were performed for two different kinds of polymers (low density polyethylene and a polyimide (6FDA-TMPD) during sorption of various vapors (hexane, cyclohexane, benzene, acrylic acid, methyl acrylate, water and oxygen). The vapor sorption affected the long-lived component (ortho-positronium component) in a systematic way regardless of the kind of the vapor molecules, i.e. for the polyethylene both the lifetime and the intensity of the long-lived component were enhanced, while for the polyimide they were decreased significantly. These different effects are interpreted in terms of different states of sorbed molecules in rubbery (the polyethylene) and in glassy (the polyimide) polymers. (Author)