Positron lifetime and coincidence Doppler broadening spectra for porous silica calcined at temperatures from 900 to 1500 oC have been measured. As the sintering temperatures increasing from 900 to 1000 oC, the height of the peaks of the ratio curves decrease, and the τ3 increases, which is due to the exclusion of the gas and the organic substance out of the cavities. As the sintering temperatures increasing from 1000 to 1250 oC, some of the defects were recovered, the grains of low quarts appearing and growing. This gives rise to the increase of the height of the peak of the ratio curve, and the decrease of lifetime (τ1,τ2 and τ3). As the sintering temperatures increasing from 1250 to 1500oC, the height of the peak of the ratio curve decreases, and the lifetime increases due to the phase transition of low quartz to cristobalite.