Positron annihilation spectroscopy, when combined with supporting high-quality modeling of positron states and annihilation in matter, is a powerful tool for detailed defect identification of vacancy-type defects in semiconductors and oxides. Here we demonstrate that the Doppler broadening of the positron annihilation radiation is a very sensitive means for observing the oxygen environment around cation vacancies, the main open-volume defects trapping positrons in measurements made for transparent semiconducting oxides. Changes in the positron annihilation signal due to external manipulation such as irradiation and annealing can be correlated with the associated changes in the sizes of the detected vacancy clusters. Our examples for ZnO, In2O3 and SnO2 demonstrate that oxygen vacancies in oxides can be detected directly using positron annihilation spectroscopy when they are complexed with cation vacancies.