Off-stoichiometric copper chromium delafossites demonstrate the highest values of electric conductivity among the p-type transparent conducting oxides. Morphological and structural changes in Cu0.66Cr1.33O2 upon annealing processes are investigated. Chained copper vacancies were previously suggested as source of the high levels of doping in this material. High resolution Helium Ion Microscopy, Secondary Ion Mass Spectrometry and Transmission Electron Microscopy reveal a significant rearrangement of copper and chromium after the thermal treatments. Furthermore, Positron Annihilation Spectroscopy evidences the presence of vacancy defects within the delafossite layers which can be assigned to the Cu vacancy chains whose concentration decreases during the thermal process. These findings further confirm these chained vacancies as source of the p-type doping and suggest that the changes in electrical conductivities within the off-stoichiometric copper based delafossites are triggered by elemental rearrangements.