Doppler broadening positron annihilation spectroscopy depth profiles were collected on photochromic YOxHy thin films. In situ UV illumination of photochromic semiconductor YOxHy films leads to an increase in S-parameter and a large reduction in W-parameter, possibly caused by a change in the charge state of vacancies or the growth of hydrogen-rich metallic Y(Ox)Hy clusters, albeit that vacancy formation or changes in positronium formation during illumination might also play a role. Intriguingly, both the S- and W-parameters increase during thermal bleaching, indicating that another process takes place. The Doppler parameters do not return to their initial values after complete thermal bleaching, suggesting that persistent local rearrangements of vacancies and possibly hydride ions have occurred during the full photodarkening-thermal bleaching cycle. Positron annihilation lifetime spectroscopy shows that a small fraction of positronium is formed in as-deposited YOxHy films, indicating that the films contain some nanopores.