Pore formation in Vycor glass subjected to annealing at 530°C and 550°C for different periods of time ranging from 4 to 48h was studied. The o-Ps lifetime in such a medium was in the range 60–100ns, while the intensity of this component varied from 20%to 28%. The values of pore radii extracted from PALS data agreed well with those from other porosimetric methods if ΔR applied in cylindrical model calculations was about 0.18nm.