Positron annihilation lifetime and Doppler broadening of annihilation line techniques have been used to obtain information about the small pore structure and size of porous SiO2 thin film produced by sputtered A1-Si thin film and etched Al-Si thin film. The film is prepared by an Al/Si 75:25 at.-% (A175Si25) target with the radiofrequency (RF) power of 66 W at room temperature. A 5 wt.-% phosphoric acid solution is used to etch the A1 cylinders. All the Al cylinders dissolved in the solution after 15 h at room temperature, and the sample is subsequently rinsed in pure water. In this way, the porous SiO2 on the Si substrate is produced. From our results, the values of all lifetime components in the spectra of Al-Si thin film are less than 1 ns, but the value of one of the lifetime components in the spectra of porous SiO2 thin film is T = 7.80 ns. With these values of lifetime, RTE (Rectangular Pore Extension) model has been used to analyze the pore size.