We focus a new application of positron annihilation lifetime spectroscopy and Doppler broadening techniques at the annihilation sites have been applied on some basaltic rocks from inactive volcano related to Sana’a-Amrana volcanic Field (SAVF). A brief geologic set up and the main petrographic signature of this inactive volcano are given. To gain an insight into geological environment, open nanospaces in the well-characterized basaltic rocks were investigated by positron annihilation spectroscopy. The analysis of the lifetime spectra yielded two lifetime components. The olivine basalt samples contain less mono- vacancies than those found in the trachybasalt and vesicular basalt samples. The overall defect (vacancy) concentration and its variation in the samples were estimated using the mean positron lifetime (τm). The Doppler broadening parameters (S and W-Parameters) were measured. A little variation of the S-parameter values has been observed for all the studied samples indicating that the valance electron contribution to annihilation is not significant.