Variable-energy positron annihilation spectroscopy has been applied to the study of defects in TiO 2 /p + -Si structures, in the as-grown state and after annealing in vacuum and in hydrogen, to investigate whether annealing (and film thickness) resulted in an increase of vacancy-type defects in the oxide films. It was found that the concentration of such defects remained unchanged after vacuum annealing for all films studied, but after H 2 annealing more than doubled for 150nm-thick films, and increased by an order of magnitude for 100nm-thick films. The nature of the vacancies was examined further by measuring high-precision annihilation lines and comparing them with a reference Si spectrum. The changes observed in the ratio spectra associated with oxygen electrons suggest that the defects are oxygen vacancies, which have been shown to enhance electroluminescence from TiO 2 /p + -Si heterostructure-based devices.