The positron annihilation lifetime spectroscopy was applied to study the porous Vycor glass annealed at the temperatures between 950 and 1050 K. With increased temperature the spectra show significant decrease in o-Ps lifetime and intensity in the pores, while the rise of intensity in the small intermolecular voids is observed. Similar changes are observed as a function of annealing time at fixed temperature depending on the time and temperature of thermal treatment. They can originate from partial crystallization of the silica in the material under study