Positron annihilation lifetime (PAL) experiments are performed in polycarbonate (PC) exposed to CO2 and He gases as a function of time and pressure. In PC/CO2 systems, hole size and fraction reduced from PAL data increase as a function of CO2 pressure and exposure time. Significant hysteresis in positron lifetime data is observed during CO2 abasorption/desorption. In PC/He systems, no variation is observed. Hole size distribution in the CO2-exposed polymers is found to be significantly broader than in unexposed samples. The high sensitivity of PAL results to CO2 exposure of PC is thought to relate to the microstructural changes in the polymer matrix, such as penetrant plasticization, gas hydrostatic pressure effect, and molecular filling and creation of holes.